U.S. patent number 10,268,289 [Application Number 15/406,202] was granted by the patent office on 2019-04-23 for conductive film and display device provided with touch panel.
This patent grant is currently assigned to FUJIFILM Corporation. The grantee listed for this patent is FUJIFILM Corporation. Invention is credited to Hiroaki Sata.
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United States Patent |
10,268,289 |
Sata |
April 23, 2019 |
Conductive film and display device provided with touch panel
Abstract
An object of the present invention is to provide a conductive
film including a polarizer in which performance deterioration of
the polarizer is suppressed while suppressing cracking of the
polarizer due to a change in moisture heat environment; and a
display device provided with a touch panel including the conductive
film. The conductive film of the present invention includes a
polarizer; and a conductive layer which is disposed on the
polarizer and includes fullerene functionalized carbon
nanotubes.
Inventors: |
Sata; Hiroaki (Kanagawa,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
N/A |
JP |
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Assignee: |
FUJIFILM Corporation (Tokyo,
JP)
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Family
ID: |
55078411 |
Appl.
No.: |
15/406,202 |
Filed: |
January 13, 2017 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20170131804 A1 |
May 11, 2017 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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PCT/JP2015/069647 |
Jul 8, 2015 |
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Foreign Application Priority Data
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Jul 17, 2014 [JP] |
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2014-147205 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B
3/00 (20130101); G02B 1/14 (20150115); B32B
27/325 (20130101); B32B 9/007 (20130101); H01B
5/14 (20130101); B32B 27/308 (20130101); G02B
5/3083 (20130101); G06F 3/0412 (20130101); G06F
3/041 (20130101); B32B 27/306 (20130101); B32B
27/36 (20130101); B32B 9/045 (20130101); B32B
23/20 (20130101); H01B 1/04 (20130101); B32B
9/00 (20130101); B32B 7/02 (20130101); B32B
27/20 (20130101); G02B 5/3033 (20130101); G06F
3/044 (20130101); B32B 27/08 (20130101); B32B
27/302 (20130101); G02F 2202/28 (20130101); B32B
2457/208 (20130101); B32B 2264/0278 (20130101); B32B
2264/102 (20130101); G02F 1/133528 (20130101); B32B
2307/42 (20130101); B29D 11/00644 (20130101); B32B
2255/26 (20130101); G02F 2202/16 (20130101); H01L
51/0048 (20130101); H01L 27/323 (20130101); G06F
2203/04103 (20130101); H01L 51/0046 (20130101); B32B
2264/025 (20130101); B32B 2307/202 (20130101); B32B
2264/0235 (20130101); B32B 2307/412 (20130101); G02F
1/13338 (20130101); B32B 2264/105 (20130101); B32B
2250/44 (20130101); H01L 51/5281 (20130101); B32B
2307/21 (20130101); B32B 2457/20 (20130101); B32B
2264/0242 (20130101) |
Current International
Class: |
G06F
3/041 (20060101); B32B 7/02 (20190101); B32B
9/00 (20060101); H01B 5/14 (20060101); H01B
1/04 (20060101); B32B 9/04 (20060101); B32B
23/20 (20060101); B32B 27/08 (20060101); B32B
27/20 (20060101); B32B 27/30 (20060101); B32B
27/32 (20060101); B32B 27/36 (20060101); G02B
5/30 (20060101); G02B 1/14 (20150101); B32B
3/00 (20060101); G06F 3/044 (20060101); H01L
51/00 (20060101); H01L 27/32 (20060101); B29D
11/00 (20060101); G02F 1/1333 (20060101); H01L
51/52 (20060101); G02F 1/1335 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1595249 |
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Mar 2005 |
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CN |
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101842317 |
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Sep 2010 |
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CN |
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2008-009750 |
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Jan 2008 |
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JP |
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2011-505312 |
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Feb 2011 |
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JP |
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4691205 |
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Feb 2011 |
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JP |
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2013-041566 |
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Feb 2013 |
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JP |
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Other References
Machine-generated English-language translation of JP 2008009750A.
cited by examiner .
International Search Report issued in PCT/JP2015/069647 dated Oct.
6, 2015. cited by applicant .
Notification of Reasons for Refusal issued by the Japanese
Intellectual Property Office dated Aug. 29, 2017, in connection
with Japanese Patent Application No. 2014-147205. cited by
applicant .
International Preliminary Report on Patentability issued by WIPO
dated Jan. 26, 2017, in connection with International Patent
Application No. PCT/JP2015/069647. cited by applicant .
Office Action Issued by the State Intellectual Property Office of
People's Republic of China, dated Oct. 29, 2018 in connection with
Chinese Patent Application No. 201580038567.0. cited by
applicant.
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Primary Examiner: Nguyen; Vu A
Attorney, Agent or Firm: Edwards Neils, LLC Edwards, Esq.;
Jean C.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of PCT International Application
No. PCT/JP2015/069647 filed on Jul. 8, 2015, which was published
under PCT Article 21(2) in Japanese, and which claims priority
under 35 U.S.C. .sctn. 119(a) to Japanese Patent Application No.
2014-147205 filed on Jul. 17, 2014. The above applications are
hereby expressly incorporated by reference, in their entirety, into
the present application.
Claims
What is claimed is:
1. A conductive film comprising: a polarizer; a conductive layer
which is disposed directly on the polarizer and includes fullerene
functionalized carbon nanotubes; and a hard coat layer which is
disposed on the conductive layer.
2. The conductive film according to claim 1, wherein a sheet
resistance value is in a range of 10 to 150 .OMEGA./.
3. The conductive film according to claim 1, wherein a thickness of
the polarizer is in a range of 5 to 30 .mu.m.
4. The conductive film according to claim 2, wherein a thickness of
the polarizer is in a range of 5 to 30 .mu.m.
5. A conductive film comprising: a polarizer; a .lamda./4 plate; a
conductive layer which is disposed directly on the .lamda./4 plate
and includes fullerene functionalized carbon nanotubes; and a hard
coat layer which is disposed on the conductive layer.
6. The conductive film according to claim 5, wherein a sheet
resistance value is in a range of 10 to 150 .OMEGA./.
7. The conductive film according to claim 5, wherein a thickness of
the polarizer is in a range of 5 to 30 .mu.m.
8. The conductive film according to claim 1, further comprising: a
protective film which is disposed on a surface of the polarizer on
the opposite side to the conductive layer side.
9. The conductive film according to claim 2, further comprising: a
protective film which is disposed on a surface of the polarizer on
the opposite side to the conductive layer side.
10. The conductive film according to claim 3, further comprising: a
protective film which is disposed on a surface of the polarizer on
the opposite side to the conductive layer side.
11. The conductive film according to claim 5, further comprising: a
protective film which is disposed on a surface of the polarizer on
the opposite side to the conductive layer side.
12. The conductive film according to claim 1, which is used for a
touch panel.
13. The conductive film according to claim 2, which is used for a
touch panel.
14. A display device provided with a touch panel comprising: the
conductive film according to claim 12.
15. A display device provided with a touch panel comprising: the
conductive film according to claim 13.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a conductive film and a display
device provided with a touch panel.
2. Description of the Related Art
In recent years, touch panel functions have been provided for
portable liquid crystal terminals typified by smartphones and other
liquid crystal display devices. Liquid crystal display devices for
which such touch panel functions are provided are mainly of
external types formed by attaching a touch panel onto a liquid
crystal display device in the related art.
Since a liquid crystal display device and a touch panel are
separately produced and then integrated an external type thereof
has a problem in that the thickness or the weight is increased.
In order to solve such a problem (the thickness or the weight) of
the external type, a so-called on-cell type liquid crystal display
device provided with a touch panel in which a conductive layer for
a touch panel is incorporated between a liquid crystal cell and a
polarizer of the liquid crystal display device (for example,
JP2008-009750A) has been disclosed. JP2008-009750A discloses an
embodiment in which a conductive layer for a touch panel is
disposed on a polarizing plate and an indium tint oxide (ITO) layer
as the conductive layer for a touch panel.
Further, due to recent demands for reduction in film thickness and
cost reduction of a liquid crystal display device, a reduction in
film thickness of members and a reduction in the number of members
of a smart phone or the like used in small and medium-sized markets
have been studied. A polarizer of the related art has a
configuration in which protective films are bonded to the front and
back surfaces of the polarizer, but products from which protective
films on one or both surfaces are removed have been developed due
to the above-described demands (for example, JP4691205B).
SUMMARY OF THE INVENTION
During production of an ITO layer, a dry process such as vacuum
deposition or sputtering accompanied by a high-temperature heat
treatment is employed, but warpage or decomposition of a polarizing
plate and volatilization of low-molecular weight components
contained in the polarizing plate easily occur and thus the
transmittance or the polarization degree of the polarizing plate is
easily degraded when an ITO layer is intended to be produced on the
polarizer according to a dry process.
Further, as in JP4691205B, a polarizing plate from which protective
films on one or both surfaces of a polarizer are removed has a
problem in that cracks easily occur due to a change in moisture
heat environment. Therefore, when a combination with a conductive
layer for a touch panel as in JP2008-009750A is used, it is desired
to suppress such problems.
The present invention has been made in consideration of the
above-described circumstances, and an object thereof is to provide
a conductive film including a polarizer in which performance
deterioration of the polarizer is suppressed while suppressing
cracking of the polarizer due to a change in moisture heat
environment.
Further, another object of the present invention is to provide a
display device provided with a touch panel which includes the
above-described conductive film.
The present inventors conducted intensive research on the problems
of the related art and found that the above-described problems can
be solved using a conductive layer that includes fullerene
functionalized carbon nanotubes.
That is, the present inventors found that the above-described
problems can be solved by the following configuration.
(1) A conductive film comprising: a polarizer; and a conductive
layer which is disposed on the polarizer and includes fullerene
functionalized carbon nanotubes.
(2) The conductive film according to (1), further comprising: a
hard coat layer which is disposed on the conductive layer.
(3) The conductive film according to (1) or (2), in which the sheet
resistance value is in a range of 10 to
150.OMEGA./.quadrature..
(4) The conductive film according to any one of (1) to (3), in
which the thickness of the polarizer is in a range of 5 to 30
.mu.m.
(5) The conductive film according to any one of (1) to (4), further
comprising: a .lamda./4 plate which is disposed between the
polarizer and the conductive layer.
(6) The conductive film according to any one of (1) to (5), further
comprising: a protective film which is disposed on the surface of
the polarizer on the opposite side to the conductive layer
side.
(7) The conductive film according to any one of (1) to (6), which
is used for a touch panel.
(8) A display device provided with a touch panel comprising: the
conductive film according to (7).
According to the present invention, it is possible to provide a
conductive film including a polarizer in which performance
deterioration of the polarizer is suppressed while suppressing
cracking of the polarizer due to a change in moisture heat
environment.
Further, according to the present invention, it is possible to
provide a display device provided with a touch panel which includes
the above-described conductive film.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view schematically illustrating a liquid
crystal display device provided with a touch panel according to a
first embodiment of the present invention.
FIG. 2 is a plan view schematically illustrating a touch panel.
FIG. 3 is an enlarged sectional view taken along the cutting line
A-A of FIG. 2.
FIG. 4 is a sectional view schematically illustrating a liquid
crystal display device provided with a touch panel according to a
second embodiment of the present invention.
FIG. 5 is a plan view schematically illustrating a laminate X.
FIG. 6 is a plan view schematically illustrating a laminate Y.
FIG. 7 is a sectional view schematically illustrating a liquid
crystal display device provided with a touch panel according to a
third embodiment of the present invention.
FIG. 8 is a sectional view schematically illustrating an organic
electroluminescence (EL) display device provided with a touch panel
according to one embodiment.
FIG. 9 is a sectional view schematically illustrating an organic EL
display device provided with a touch panel according to another
embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, a conductive film and a display device provided with a
touch panel of the present invention will be described in
detail.
In the present specification, the numerical ranges shown using "to"
indicate ranges including the numerical values described before and
after "to" as the lower limits and the upper limits. Moreover, the
views of the present invention are schematic views and the
relationships in thickness of each layer or positional
relationships do not necessarily coincide with the actual ones.
One feature point of the conductive film of the present invention
is that a conductive layer containing fullerene functionalized
carbon nanotubes is used. As described later in detail, fullerene
functionalized carbon nanotubes includes one or plural fullerenes
and/or fullerene-based molecules covalently bonded to carbon
nanotubes. A fullerene functionalized carbon nanotube is a material
that has mechanical flexibility derived from carbon nanotubes and
exhibits excellent conductivity more than carbon nanotubes as a
result of adding a fullerene functional group. In the conductive
layer, a network structure is easily formed while fullerene
functionalized carbon nanotubes are entangled with each other, and
a fullerene functional group comes into contact with a fullerene
functionalized carbon nanotube adjacent to the fullerene functional
group to obtain a conductive layer exhibiting excellent conduction
characteristics.
Moreover, as described later, when a conductive layer containing
fullerene functionalized carbon nanotubes is prepared, high
temperature vacuum conditions are not required. Accordingly,
compared to a case where an ITO film is prepared by a dry process,
performance degradation of a polarizer can be suppressed.
In addition, as described above, cracks easily occur in the
polarizer which does not have a protective film on one or both
sides due to the moisture heat environment. One main reason is that
the polarizer is repeatedly swollen or contracted due to a change
in moisture heat environment. On the contrary, since fullerene
functionalized carbon nanotubes are entangled with each other in
the conductive layer, the conductive layer itself is unlikely to be
swollen or contracted. Accordingly, it is assumed that the swelling
and contracting of the polarizer are suppressed and thus occurrence
of cracks of the polarizer is suppressed when such a conductive
layer and the polarizer are combined with each other.
In other words, it is possible to dispose the conductive layer
containing the fullerene functionalized carbon nanotubes on the
polarizer while suppressing performance deterioration of the
polarizer and to suppress occurrence of cracks of the polarizer due
to a change in moisture heat environment.
The conductive film of the present invention includes at least a
polarizer and a conductive layer which is disposed on the polarizer
and contains fullerene functionalized carbon nanotubes.
Hereinafter, members (the polarizer and the conductive layer)
included in the conductive film will be described in detail.
<Polarizer>
The polarizer may be a member having a function of converting light
into specific linearly polarized light and an absorptive type
polarizer or a reflective type polarizer can be used.
Examples of the absorptive type polarizer include an iodine-based
polarizer, a dye-based polarizer using a dichroic dye, and a
polyene-based polarizer. A coating type polarizer and a stretching
type polarizer may be exemplified as the iodine-based polarizer and
the dye-based polarizer and both can be used, but a polarizer
prepared by adsorbing iodine or a dichroic dye to polyvinyl alcohol
to be stretched is preferable.
Further, examples of a method of obtaining a polarizer by
performing stretching and dyeing in a state of a laminated film
having a polyvinyl alcohol layer formed on a base include methods
described in JP5048120B, JP5143918B, JP4691205B, JP4751481B, and
JP4751486B, and a known technique related to these polarizers can
be preferably used.
Examples of the reflective type polarizer include a polarizer
formed by laminating a thin film having a different film
birefringence, a wire grid type polarizer, and polarizer obtained
by combining a cholesteric liquid crystal having a selective
reflection range with a quarter wavelength plate.
Among these, from the viewpoint of more excellent adhesiveness to
the conductive layer described below, a polarizer including a
polyvinyl alcohol-based resin (particularly, at least one selected
from the group consisting of polyvinyl alcohol and an
ethylene-vinyl alcohol copolymer) is preferable.
The thickness of the polarizer is not particularly limited, but is
preferably 35 .mu.m or less, more preferably in a range of 3 to 30
.mu.m, still more preferably in a range of 5 to 30 .mu.m, and
particularly preferably in a range of 5 to 20 .mu.m, from the
viewpoint of reducing the thickness of a display device.
In addition, the thickness thereof is an average value obtained by
measuring the thicknesses of arbitrary 10 points of the polarizer
and arithmetically averaging the values.
<Conductive Layer>
The conductive layer contains fullerene functionalized carbon
nanotubes. The fullerene functionalized carbon nanotubes will be
described below.
The content of fullerene functionalized carbon nanotubes in the
conductive layer is not particularly limited, but is preferably 60%
by mass or greater, more preferably 80% by mass or greater, and
still more preferably 90% by mass with respect to the total mass of
the conductive layer, from the viewpoints that cracks of the
polarizer due to a change in moisture heat environment are further
suppressed (hereinafter, simply also referred to as "from the
viewpoint of more excellent effects of the present invention")
and/or the conductivity of the conductive layer is more excellent.
The upper limit thereof is not particularly limited, but is
typically 100% by mass.
Further, the conductive layer may contain additives other than the
fullerene functionalized carbon nanotubes and the content thereof
is not particularly limited, but is preferably in a range of 0.01%
to 40% by mass, more preferably in a range of 0.1% to 20% by mass,
and still more preferably in a range of 0.1% to 10% by mass with
respect to the total mass of the conductive layer from the
viewpoints of more excellent effects of the present invention
and/or more excellent conductivity of the conductive layer.
The thickness of the conductive layer is not particularly limited,
but is preferably in a range of 0.1 to 15 .mu.m and more preferably
in a range of 1 to 10 .mu.m from the viewpoints of more excellent
effects of the present invention and/or more excellent conductivity
of the conductive layer. Further, the thickness thereof is an
average value obtained by measuring the thicknesses of arbitrary 10
points of the conductive layer and arithmetically averaging the
values.
The conductive layer may be disposed on the entire surface (main
surface) of the polarizer or on a region which is a part of the
surface of the polarizer. Particularly, in a case where the
conductive layer is applied to a touch panel as described below, it
is preferable that the conductive layer is disposed in a
predetermined pattern.
A method of preparing a conductive layer is not particularly
limited as long as a conductive layer containing fullerene
functionalized carbon nanotubes is prepared, and examples thereof
include a method of allowing fullerene functionalized carbon
nanotubes to be dispersed in a solvent to be applied onto a
polarizer and performing a drying treatment as needed and a method
of blowing aerosols containing fullerene functionalized carbon
nanotubes to a polarizer.
Moreover, other than a method of preparing a conductive layer
directly on a polarizer, a method of preparing a conductive layer
containing fullerene functionalized carbon nanotubes on a temporary
support and transferring the conductive layer onto a polarizer may
be exemplified.
As described above, the conductive layer may be disposed in a
predetermined pattern.
A method of forming a conductive layer in a predetermined pattern
is not particularly limited, and examples thereof include a method
of depositing a conductive layer containing fullerene
functionalized carbon nanotubes on a support (for example, a
polarizer or a temporary support) on which a mask is provided in a
predetermined pattern and removing the mask to obtain a conductive
layer having a predetermined pattern; a method of preparing a
resist having a predetermined pattern on a conductive layer and
performing etching through a wet process using a strong acid, a
chemical agent having excellent oxidizability or corrosivity, and a
strong alkali; and a method of patterning a conductive layer
through screen printing. In the present invention, it is preferable
that the conductive layer is patterned by a dry etching
process.
An example thereof is described below, but the present invention is
not limited thereto.
An aluminum film which becomes a mask is formed on a conductive
layer and then the aluminum film is coated with a resist for
forming a pattern. Next, the resist together with a pattern are
exposed to light and developed. Subsequently, the aluminum film is
etched using the patterned resist as a mask. Next, the resist is
peeled off. Further, the conductive layer exposed to the surface is
burned for removal using a dry etching device, for example, an
O.sub.2 plasma ashing device. Here, the burning is used for a
method of oxidizing using an O.sub.2 plasma and a radical activated
without increasing the substrate temperature as well as a case
where the sample temperature is increased, that is, the burning
includes ashing. Finally, the conductive layer can be patterned by
removing the aluminum film on the conductive layer through wet
etching using phosphoric acid, particularly, heated phosphoric
acid.
Moreover, the dry etching has been described using O.sub.2 plasma
ashing, but etching can be carried out using other dry etching
methods such as sputtering etching, chemical etching, reactive
etching, reactive sputtering etching, ion beam etching, and
reacting ion beam etching.
Gas etching or radical-containing etching is chemical etching or
reactive etching and is capable of removing nanoparticles mainly
containing fullerene functionalized carbon nanotubes or carbon
using reactive gas such as oxygen or hydrogen which reacts with
carbon and can be removed. The carbon bonds of fullerene
functionalized carbon nanotubes, carbon nanoparticles, or amorphous
carbon covering a catalytic metal surface are formed of 6-membered
rings or 5-membered rings, but the carbon bonds of carbon
nanoparticles or amorphous carbon covering a catalytic metal
surface are incomplete compared to fullerene functionalized carbon
nanotubes so that the amount of 5-membered rings is larger and
easily react with reactive gas.
Accordingly, in a case where a conductive layer containing carbon
nanoparticles or fullerene functionalized carbon nanotubes that
include amorphous carbon covering the catalytic metal surface is
patterned, gas etching or radical-containing etching is more
effective. Further, since gas etching or radical-containing etching
is isotropic etching, reactive gas runs around not only the surface
of nanotubes to be patterned but also the side wall or back surface
of nanotubes and nanoparticles in the vicinity of the surface and
selectively reacts with carbon so that the portion other than
catalytic metal can be rapidly removed. In addition, a conductive
layer containing fullerene functionalized carbon nanotubes that
include nanoparticles can be patterned by adding a process of
removing only the catalytic metal. For example, in a case where the
reaction product is oxygen, the reaction product becomes gas such
as CO or CO.sub.2 and thus does not re-adhere to the support.
Therefore, there is no problem of surface contamination.
Particularly, the burning using oxygen is simply carried out, which
is preferable.
Next, a case of using ionic sputtering effects is considered. For
example, aluminum is covered on a conductive layer which is
intended to be left at the time of patterning using sputtering or
vapor deposition, but aluminum is unlikely to be sufficiently
covered particularly in the inside of a concave in a case where the
surface of the conductive layer is significantly uneven. In a case
of using reactive gas, gas runs around and the conductive layer is
etched from a portion in which a protective film is not
sufficiently covered in a case where the etching time is long.
Meanwhile, since the straightness of ion species is strong and the
ion species enter from the upper surface in a case of using ionic
sputter etching, it is difficult to damage the conductive layer
positioned below the thick covered film. Further, because of
anisotropic etching, etching can be made reliably and vertically to
the mask pattern. Therefore, this is preferable for removing the
conductive layer containing fullerene functionalized carbon
nanotubes in which nanoparticles do not contain catalytic metal and
also preferable for forming a fine pattern.
In ion beam etching or reactive ion beam etching, etching can be
performed without mask, but modulation of beams and the process
time per area are required. Further, a small-sized display is
suitable here than a large area display.
Further, the example using an aluminum film as a mask during the
above-described O.sub.2 plasma ashing has been described, metals,
such as titanium, gold, molybdenum, tungsten, and silver, which do
not damage the conductive layer during the removal of the
conductive layer may be used. The conductive layer can be rapidly
removed by a mixed solution of titanium and nitric acid, gold and
aqua regia, molybdenum and hot-concentrated sulfuric acid or aqua
regia, or tungsten and hydrofluoric acid or nitric acid. However,
since the conductive layer is gradually degraded when nitric acid,
sulfuric acid, and hydrogen fluoride are used during a long-time
process, it is necessary to perform the process, particularly,
under conditions of the temperature and the concentration in a
predetermined time, which are not damaged. The process can be
performed without damage by carrying out the process at room
temperature in one hour using 65% of nitric acid, 90% of sulfuric
acid, 45% of hydrogen fluoride, and a mixture of these. Aluminum is
preferred than other metals since aluminum is inexpensive compared
to other metals and is in a state of the conductive layer being
covered, in which aluminum crystal grains are dense and the
coverage is high, and the conductive layer is not degraded with
respect to phosphoric acid which is an etching solution.
Meanwhile, a metal with a large atomic weight has a small
sputtering rate due to ions and is suitable as a mask material in a
case of dry etching mainly having sputtering effects. Particularly,
gold, tungsten, and molybdenum have resistance at least two times
the resistance of aluminum of titanium and thus are unlikely to be
damaged immediately below a mask. Therefore, it is preferable that
the conductive layer containing fullerene functionalized carbon
nanotubes in which nanoparticles do not contain catalytic metal is
removed and the removal is preferable for forming a fine
pattern.
Moreover, other than metals, silicon dioxide or aluminum oxide
which is not damaged by O.sub.2 plasma ashing and does not damage
the conductive layer during the removal can be used.
(Fullerene Functionalized Carbon Nanotubes)
The fullerene functionalized carbon nanotubes (in the present
specification, also referred to as CBFFCNT) include one or plural
fullerenes and/or fullerene-based molecules covalently bonded to
carbon nanotubes. That is, CBFFCNT is a carbon nanotube in which
one or plural kinds selected from the group consisting of
fullerenes and fullerene-based molecules are introduced through a
covalent bond.
Further, a carbon nanotube is a substance in which a six-membered
ring network (graphene sheet) resulting from carbon atoms is turned
into a coaxial tubular monolayer or multilayer. A carbon nanotube
may be configured of only carbon atoms or may include carbon atoms
and one or plural kinds of other atoms (for example, heteroatoms).
A carbon nanotube may have a cylindrical or tubular structure whose
end is open and/or closed. Moreover, a carbon nanotube may have
other kinds of carbon nanotube structures.
A fullerene is a molecule which includes carbon atoms and has a
substantially spherical, oval, or ball-like structure. A fullerene
may have a hollow structure whose surface is closed or a
substantially spherical structure whose surface is not completely
closed and which has one or plural open bonds. A fullerene may have
a substantially hemispheric shape and/or a shape of another
arbitrary sphere.
Fullerene-based molecules are any of the above-described
fullerenes, one or plural carbon atoms in a molecule are one or
plural atoms other than carbon atoms (for example, heteroatoms),
molecules, molecules substituted with groups and/or compounds, or
the above-described fullerene molecules; one or plural additional
atoms (for example, heteroatoms), molecules, molecules in which
groups and/or compounds are incorporated in fullerenes, or the
above-described fullerenes; or one or plural additional atoms (for
example, heteroatoms), molecules, or molecules in which groups
and/or compounds adhere to the surface of fullerenes.
In addition, the point in which one or plural other fullerenes can
adhere to the surface of carbon nanotubes may be mentioned, but
this is a simply one non-limiting example.
One or plural fullerenes and/or fullerene-based molecules can be
covalently bonded to the outer surface and/or inner surface of
carbon nanotubes, preferably the outer surface thereof. The
fullerenes and/or fullerene-based molecules may contain 20 to 1000
atoms. The fullerene and/or fullerene-based molecules may be
covalently bonded to carbon nanotubes through one or plural
crosslinking atomic groups or may be covalently bonded directly to
carbon nanotubes.
The crosslinking atomic groups indicate arbitrary atoms, elements,
molecules, groups, and/or compounds used to allow fullerenes and/or
fullerene-based molecules to be covalently bonded to carbon
nanotubes. Preferred crosslinking atomic groups may include
arbitrary elements of Group IV, Group V, and Group VI of the
periodic table of elements. The preferred crosslinking atomic
groups may include oxygen, hydrogen, nitrogen, sulfur, an amino
group, a thiol group, an ether group, an ester group, and/or a
carboxylic acid group, and/or other arbitrary preferred groups,
and/or derivatives thereof. The preferred crosslinking atomic
groups may include a carbon-containing group.
Further, as described above, as another option or in addition to
the above-described options, the fullerenes and/or fullerene-based
molecules may be covalently bonded directly to carbon nanotubes.
For example, the fullerenes and/or fullerene-based molecules may be
covalently bonded directly thereto through one or plural carbon
bonds.
Carbon nanotubes may include single-wall, double-wall, or
multi-wall carbon nanotubes or composite carbon nanotubes. Carbon
nanotubes can be blended in a dispersion of a gas, a liquid, and/or
a solid, a solid structure, powder, paste, and/or a colloidal
suspension, and/or can be precipitated on the surface, and/or can
be synthesized.
The fullerene functionalized carbon nanotubes can be bonded to one
or plural carbon nanotubes and/or fullerene functionalized carbon
nanotubes through one or plural fullerenes and/or fullerene-based
molecules. In other words, for example, two fullerene
functionalized carbon nanotubes can adhere to each other through
common fullerene molecules.
(Method of Producing Fullerene Functionalized Carbon Nanotubes)
A method of producing one or plural fullerene functionalized carbon
nanotubes includes allowing one or plural catalyst particles,
carbon sources, and/or reagents to come into contact with each
other to be heated in a reactor and producing one or plural carbon
nanotubes containing one or plural fullerenes and/or
fullerene-based molecules covalently bonded to one or plural carbon
nanotubes.
A step of allowing one or plural catalyst particles, carbon
sources, and/or reagents to come into contact with each other can
be performed according to an arbitrary suitable method (for
example, mixing) of bringing those into contact with each other. It
is preferable that this method is performed in a reactor. In this
manner, one or plural fullerene functionalized carbon nanotubes are
produced.
The fullerene functionalized carbon nanotubes can be produced in a
gas phase such as an aerosol and/or on a base. Further, this method
may be carried out by a continuous flow, a batch process, or a
combination of a batch sub-process and a continuous
sub-process.
When the fullerene functionalized carbon nanotubes are produced,
various carbon-containing materials can be used as carbon sources.
Further, a carbon-containing precursor that forms a carbon source
can be used. A carbon source can be selected from the group
consisting of one or plural alkanes, alkenes, alkynes, alcohols,
aromatic hydrocarbons, and arbitrary other suitable groups,
compounds, and materials. Further, a carbon source can be selected
from the group consisting of carbon compounds of a gas (methane,
ethane, propane, ethylene, acetylene, carbon monoxide, and the
like), volatile carbon sources of a liquid (benzene, toluene,
xylene, trimethylbenzene, methanol, ethanol, octanol, and the
like), other arbitrary suitable compounds, and derivatives thereof.
Thiophene can be also used as a carbon source. Among these, carbon
monoxide gas is preferable as a carbon source.
Carbon sources can be used alone or in plural kinds thereof.
In a case where a carbon precursor is used, the carbon precursor
can be activated at a desired location in a reactor using a heated
filament or plasma.
According to one embodiment, one or plural carbon sources function
as one or plural catalyst particle sources, reagents, reagent
precursors, and/or additional reagents.
5 to 10000 ccm and preferably 50 to 1000 ccm of a carbon source can
be introduced into a reactor at a rate of approximately 300 ccm.
The pressure of various materials (for example, carbon sources)
used for this method can be set to be in a range of 0.1 to 1000 Pa
and preferably in a range of 1 to 500 Pa.
One or plural reagents can be used for producing fullerene
functionalized carbon nanotubes. A reagent may be an etching agent.
A reagent can be selected from the group consisting of hydrogen,
nitrogen, water, carbon dioxide, nitrous oxide, nitrogen dioxide,
and oxygen. Further, a reagent can be selected from organic and/or
inorganic oxygen-containing compounds (ozone (O.sub.3) and the
like) and various hydrides. One or plural reagents used for this
method can be selected from carbon monoxide, octanol, and/or
thiophene.
A preferable reagent (one or plural kinds) is water vapor and/or
carbon dioxide. Further, other arbitrary suitable reagents can be
used for the method of the present invention. Other reagents and/or
reagent precursors can be used as carbon sources. On the contrary,
carbon sources can be used as reagents and/or reagent precursors.
Examples of such reagents include ketone, aldehyde, alcohol, ester,
and/or ether, and/or other arbitrary suitable compounds.
One or plural reagents and/or reagent precursors can be introduced
into a reactor together with or separately from carbon sources. One
or plural reagents and reagent precursors can be introduced into a
reactor at a concentration of 1 to 12000 ppm and preferably 100 to
2000 ppm.
The concentration of one or plural fullerenes and/or
fullerene-based molecules covalently bonded to carbon nanotubes.
The concentration thereof can be adjusted by adjusting the amount
(for example, the concentration) of one or plural reagents being
used, adjusting the heating temperature, and/or adjusting the
retention time. The adjustment is performed according to a
synthesis method. The heating can be performed at a temperature of
250.degree. C. to 2500.degree. C. and preferably 600.degree. C. to
1000.degree. C. For example, in a case where H.sub.2O and CO.sub.2
are used as reagents, the concentration of a reagent in a case of
water can be set to be in a range of 45 to 245 ppm and preferably
in a range of 125 to 185 ppm and the concentration of a reagent in
a case of CO.sub.2 can be set to be in a range of 2000 to 6000 ppm
and preferably approximately 2500 ppm. In this manner, the
fullerene density higher than 1 fullerene/nm can be set. Even at a
specific concentration of one or plural reagents, it is possible to
find an optimum range of the heating temperature.
Various catalyst materials (catalyst particles) that catalyze
decomposition and disproportionation of carbon sources can be
used.
Catalyst particles being used may contain, for example, various
metals and/or non-metallic materials. Preferable catalyst particles
contain one metal and preferably one transition metal and/or metals
(plural kinds) and/or a combination of transition metals (plural
kinds). It is preferable that catalyst particles contain iron,
cobalt, nickel, chromium, molybdenum, palladium, and/or other
arbitrary similar elements. The catalyst particles can be formed by
thermal decomposition of ferrocene vapor from a chemical precursor
(for example, ferrocene). The catalyst particles can be produced by
heating a metal or a metal-containing material.
The catalyst particles and the catalyst precursor can be introduced
into a reactor at a ratio of 10 to 10000 ccm and preferably 50 to
1000 ccm (for example, approximately 100 ccm).
The catalyst particles used for the method of the present invention
can be produced using various methods. Examples of such methods
include chemical vapor decomposition of a catalyst precursor and
physical vapor nucleation. Further, as other methods, catalyst
particles can be produced from liquid droplets formed from a metal
salt solution and a colloidal metal nanoparticle solution using
electrospray, ultrasonic spray, or air spray or can be produced
using thermal drying and decomposition, and/or other arbitrary
applicable methods, and/or processes, and/or materials. Other
arbitrary procedures for producing particles, for example,
adiabatic expansion in a nozzle, arc discharge, and/or an
electrospray system can be used to form catalyst particles. A hot
wire generator can be used to produce catalyst particles. According
to the present invention, other means for heating and/or
evaporating a mass containing a metal used to generate metal vapor
can be used.
The catalyst particles can be synthesized in advance and then can
be introduced into a reactor. However, since particles having a
particle size range required for production of CBFFCNT are
difficult to handle and/or store, it is preferable that particles
are produced in the vicinity of the reactor as an integrating step
in the producing process.
Aerosols and/or catalyst particles carrying the surface can be used
to produce fullerene functionalized carbon nanotubes. A catalyst
particle precursor can be used to produce catalyst particles.
In a case of producing fullerene functionalized carbon nanotubes
carrying a base, catalyst particles can be directly produced on the
base and can be precipitated from a gas phase due to diffusion,
thermophoresis, electrophoresis, inertial impaction, and/or other
arbitrary means.
In a case of a chemical production method of catalyst particles, a
metal organic compound, an organic metal compound, and/or an
inorganic compound such as a metallocene compound, a carbonyl
compound, a chelate compound, and/or other arbitrary suitable
compounds can be used as a catalyst precursor.
In a case of a physical production method of catalyst particles,
for example, a pure metal or an alloy thereof is evaporated using
resistance heating, induction heating, plasma heating, conductive
heating, or radiative heating, or various energy sources such as a
chemical reaction (here, the concentration of generated catalyst
vapor is lower than the level required for nucleation at a location
of release) and then nucleation, condensation, and/or coagulation
can be made from supersaturated vapor. As means for generating
supersaturated vapor leading to formation of catalyst particles in
the physical method, gas cooling using convective heat transfer,
conductive heat transfer, and/or radiant heat transfer, and/or
adiabatic expansion (for example, in a nozzle) in the periphery of
a wire which is resistance-heated may be exemplified.
In a case of a thermal decomposition production method of catalyst
particles, for example, various metals and/or other arbitrary
suitable materials of inorganic salts such as nitrate, carbonate, a
chloride, and/or a fluoride.
The method of present invention may further include a step of
introducing one or plural additional reagents. Additional reagents
are used to promote formation of carbon nanotubes, change the
decomposition rate of carbon sources, react with amorphous carbon
during and/or after production of carbon nanotubes, and/or react
with carbon nanotubes (for example, for purification of carbon
nanotubes, doping, and/or further functionalization). Additional
reagents used to associate with chemical reactions with catalyst
particle precursors, catalyst particles, carbon sources, amorphous
carbon, and/or carbon nanotubes (to which one or plural fullerene
and/or fullerene-based molecules are covalently bonded) can be used
according to the present invention. One or plural additional
reagents can be introduced together with or separately from carbon
sources.
As accelerators (that is, additional reagents) for forming CBFFCNT
of the present invention, additional reagents such as sulfur,
phosphorus, and/or nitrogen elements, and/or compounds of these
(thiophene, PH.sub.3, NH.sub.3, and the like) can be used. The
additional accelerator reagents can be selected from H.sub.2O,
CO.sub.2, NO, and/or arbitrary other suitable elements, and/or
compounds.
In some cases, during a purification process, for example,
undesirable amorphous carbon coating and/or catalyst particles
encapsulated in CBFFCNT are required to be removed. In this present
invention, it is possible to provide one or plural separate
reactors to be heated and reactor sections and one reactor or one
section of the reactor is used to produce CBFFCNT, and the rest
(one or plural) are used for further purification, further
functionalization, and/or doping. The above-described steps may be
combined with each other.
As chemical materials for removing amorphous carbon, an arbitrary
compound, a derivative of the compound, and/or a decomposition
product of the compound (formed in a reactor instantly) can be used
and the chemical substance does not react with graphite carbon but
with preferably amorphous carbon. As examples of such reagents, one
or plural alcohols, ketones, organic acids, and/or inorganic acids
can be used. Further, oxidants such as H.sub.2O, CO.sub.2, and/or
NO can be used. According to the present invention, other
additional reagents can be also used.
According to one embodiment, one or plural additional reagents can
be used for further functionalization of CBFFCNT. The properties of
CBFFCNT to be produced are changed by chemical groups and/or
nanoparticles adhering to CBFFCNT. When CBFFCNT is doped by boron,
nitrogen, lithium, sodium, and/or potassium elements, the
conductivity of CBFFCNT is changed. That is, CBFFCNT having
superconductivity is obtained. When carbon nanotubes are
functionalized by fullerenes, further functionalization of carbon
nanotubes becomes possible due to the adhering fullerenes. In the
present invention, when appropriate reagents are introduced before,
during, and/or after formation of CBFFCNT, functionalization and/or
doping can be performed instantly.
According to one embodiment, one or plural additional reagents can
be used as carbon sources, carrier gas, and/or catalyst particle
sources.
According to one embodiment, this method further includes a step of
producing fullerene functionalized carbon nanotube composite
materials by introducing one or plural additives into a reactor.
For example, one or plural additives can be used to be applied to
CBFFCNT and/or to be mixed with CBFFNCT to produce a CBFFCNT
composite material. An object of the additive is to increase
catalyst efficiency of CBFFCNT adhering to a matrix and/or to
control properties the matrix (hardness, stiffness, chemical
reactivity, optical characteristics, and/or thermal conductivity,
and/or electrical conductivity, and/or an expansion coefficiency).
As coating or aerosolized particle additives for a CBFFCNT
composite material, preferably, one or plural metal-containing
material, and/or organic materials (polymer and the like), and/or
ceramics, solvents, and/or aerosols of these can be used. According
to the present invention, other arbitrary suitable additives can be
used.
For example, the obtained composite material can be directly
recovered, adhere to a matrix, and/or adhere to the surface. This
can be carried out using electric force, thermophoretic force,
inertial force, diffusing force, turbophoretic force, gravity,
and/or other suitable forces to form a thick film or a thin film,
yarn, a structural body, and/or a layered material. CBFFCNT can be
coated with one or more solids or liquids to be added and/or solids
or liquid particles to form a CBFFCNT composite material.
The additive is mixed and aggregated in a gas phase to adhere to
the surface of CBFFCNT as a surface coating using condensation of
supersaturated vapor, a chemical reaction with a layer having
adhered in advance, a doping agent, and/or a functional group,
and/or other means, alternatively, in a case where the additive is
in the form of particles. Further, it is possible to combine
adhesion of gas and particles to CBFFCNT.
According to one embodiment, if necessary, one or plural carrier
gases can be used to introduce the above-described materials into a
reactor. If desired, the carrier gases may function as carbon
sources, catalyst particle sources, reagent sources, and/or
additional reagent sources.
According to one embodiment, this method further includes a step of
recovering produced one or plural fullerene functionalized carbon
nanotubes and/or fullerene functionalized carbon nanotube composite
materials as a solid, a liquid, a dispersion of gas, a solid
structure, powder, paste, a colloidal suspension, and/or a surface
deposit.
According to one embodiment, this method further includes a step of
allowing a dispersion of produced fullerene functionalized carbon
nanotubes and/or fullerene functionalized carbon nanotube composite
material, for example, a gas dispersion to adhere to the surface,
and/or a matrix, and/or a layered structure, and/or a device.
The adhesion of the synthesized material is controlled by various
means (inertial impaction, thermophoresis, and/or movement in an
electric field, but not limited to these) so that the material is
formed in a desired shape (for example, yarn, points, or a
three-dimensional structure) with desirable properties such as
electrical conductivity and/or thermal conductivity, opacity and/or
mechanical strength, and hardness and/or ductility. Examples of
means for controlling adhesion of the synthesized material include
gravitational settling, fiber and barrier filtration, inertial
impaction, thermophoresis, and/or movement in an electric field,
which form the material in a desired shape (for example, yarn,
points, or a film) with desirable properties such as electrical
conductivity and/or thermal conductivity, opacity and/or mechanical
strength, and hardness and/or ductility, but the means is not
limited to these.
Hereinafter, a device used to produce one or plural fullerene
functionalized carbon nanotubes will be described. This device
includes a reactor used for heating one or plural catalyst
particles, carbon sources, and/or reagents, and the heating is
performed to produce one or plural carbon nanotubes containing one
or plural fullerene and/or fullerene-based molecules covalently
bonded to one or plural carbon nanotubes.
Such a device may further includes one or more selected from means
for producing catalyst particles; means for introducing one or
plural catalyst particles; means for introducing one or plural
catalyst particle precursors; means for introducing one or plural
carbon sources; means for introducing one or plural carbon source
precursors; means for introducing one or plural reagents; means for
introducing one or plural reagent precursors; means for introducing
one or plural additional reagents; means for introducing one or
plural additives; means for recovering one or plural produced
fullerene functionalized carbon nanotubes and/or fullerene
functionalized carbon nanotube composite materials; means for
adhering a dispersion (for example, a gas dispersion) of produced
fullerene functionalized carbon nanotubes and/or carbon nanotube
composite materials; means for producing catalyst particles; and/or
means for supplying energy to a reactor. For example, the means
used to introduce the above-described various materials to other
arbitrary portions of the reactor and/or the device may include one
same means or various means. For example, according to one
embodiment of the present invention, one or plural carbon sources
and reagents can be introduced into the reactor using one same
means. Further, if necessary, the device may include mixing means
in the reactor.
The device may include one or plural reactors and, accordingly, it
is possible to carry out continuous production and/or batch
production of composite materials of CBFFCNT, further
functionalized CBFFCNT, doped CBFFCNT, and/or CBFFCNT of these. The
reactors are configured in series and/or juxtaposition so that
various final compositions can be obtained. Further, the reactors
can be operated by complete batch procedures or partial batch
procedures.
The reactor may include a tube having ceramic materials, iron,
stainless steel, and/or other arbitrary suitable materials. In one
embodiment of the present invention, the surface of the reactor may
be formed to include materials used to catalytically produce one or
plural reagents required for production of CBFFCNT from one or
plural reagent precursors introduced into the reactor (for example,
in the upstream).
In one embodiment, the internal diameter of the tube can be set to
be in a range of, for example, 0.1 to 200 cm and preferably in a
range of 1.5 to 3 cm and the length of the tube can be set to be in
a range of, for example, 1 to 2000 cm and preferably in a range of
25 to 200 cm. Other arbitrary dimensions (for example, those used
for industrial usage) can be applied.
In a case of using the device of the present invention, the
operating pressure in the reactor can be set to be in a range of,
for example, 0.1 to 10 atm and preferably in a range of 0.5 to 2
atom (for example, approximately 1 atm). Further, the temperature
in the reactor can be set to be in a range of, for example, 250 to
2500.degree. C. and preferably in a range of 600.degree. C. to
1000.degree. C.
The means for producing catalyst particles may include a
pre-reactor. This means may include a hot wire generator. The
device may further include other arbitrary suitable means for
producing catalyst particles. This means can be separated from the
reactor at a distance. Alternatively, this means may be used as a
part incorporated in the reactor. In a case of using the device of
the present invention, the means for producing catalyst particles
can be placed at a position in which the temperature of the reactor
is in a range of 250.degree. C. to 2500.degree. C. and preferably
in a range of 350.degree. C. to 900.degree. C.
According to one preferred embodiment, for example, a flow passing
through a pre-reactor (for example, a hot wire generator) is a
mixture of, preferably, hydrogen and nitrogen and the rate of
hydrogen here is preferably in a range of 1% to 99%, more
preferably in a range of 5 to 50%, and most preferably
approximately 7%. The flow rate, for example, the flow rate passing
through the hot wire generator can be set to be in a range of 1 to
10000 ccm and preferably in a range of 250 to 600 ccm.
According to the present invention, it is possible to promote
and/or inhibit the chemical reaction and/or CBFFCNT synthesis using
various energy sources. Examples thereof include a reactor heated
by resistance, conduction, radiation, and/or atomic power, and/or
the chemical reaction and/or a pre-reactor, but the examples are
not limited to these. Other energy sources can be used as a reactor
and/or a pre-reactor. For example, induction heating using a high
frequency, a microwave, sound, or a laser and/or any other energy
sources (chemical reaction and the like) can be used.
<Other Members>
The above-described conductive film may include members other than
the polarizer and the conductive film. Hereinafter, arbitrary
constituent members will be described in detail.
<Hard Coat Layer>
The conductive film of the present invention may include a hard
coat layer on the conductive layer (on the surface of the
conductive layer on the opposite side to the polarizer side) as a
functional layer.
In the present invention, the hard coat layer is a layer in which
the pencil hardness of the conductive film is increased by being
formed. Practically, the pencil hardness (JIS K5400) of the
conductive film after the hard coat layer is laminated is
preferably H or greater, more preferably 2H or greater, and most
preferably 3H or greater.
The thickness of the hard coat layer is preferably in a range of
0.4 to 35 .mu.m, more preferably in a range of 1 to 30 .mu.m, and
still more preferably in a range of 1.5 to 20 .mu.m.
The hard coat layer may be a single layer or multiple layers. In a
case where a plurality of hard coat layers are present, it is
preferable that the total film thickness of all hard coat layers is
in the above-described range.
The surface of the hard coat layer of the conductive film according
to the present invention may be flat or uneven. Moreover, if
necessary, the hard coat layer may contain light-transmitting
particles for improving surface unevenness or providing internal
scattering.
A method of forming a hard coat layer is not particularly limited,
and a known method may be employed. Typically, a method of coating
the conductive layer with a composition for forming a hard coat
layer which contains a predetermined component and performing a
curing treatment (for example, a heat treatment and/or a light
irradiation treatment) as needed.
An embodiment of the composition for forming a hard coat layer will
be described later.
A known coating method can be employed as the coating method.
Examples thereof include gravure coating, roll coating, reverse
coating, knife coating, die coating, lip coating, doctor coating,
extrusion coating, slide coating, wire bar coating, curtain
coating, extrusion coating, and spinner coating.
After the conductive layer is coated with the composition for
forming a hard coat layer, if necessary, a drying treatment may be
performed to the layer coated with the composition in order to
remove a solvent. The method of the drying treatment is not
particularly limited, and examples thereof include an air drying
treatment and a heat treatment.
A method of polymerizing and curing the layer coated with the
composition obtained by the above-described coating is not
particularly limited, and examples thereof include a heat treatment
and a light irradiation treatment.
The conditions for the heat treatment vary depending on the
material to be used, but it is preferable that the heat treatment
is performed at 40.degree. C. to 200.degree. C. (preferably in a
range of 50.degree. C. to 150.degree. C.) for 0.5 minutes to 10
minutes (preferably in a range of 1 minute to 5 minutes) from the
viewpoint of more excellent reaction efficiency.
The conditions for the light irradiation treatment is not
particularly limited, and an ultraviolet irradiation method of
generating and applying ultraviolet rays for photocuring is
preferable. Ultraviolet lamps used for such method include a metal
halide lamp, a high-pressure mercury lamp, a low-pressure mercury
lamp, a pulsed xenon lamp, a xenon/mercury mixed lamp, a
low-pressure germicidal lamp, and an electrodeless lamp. Among
these ultraviolet lamps, a metal halide lamp or a high-pressure
mercury lamp is preferable.
In addition, the irradiation conditions vary depending on the
conditions of each lamp, but the irradiation exposure quantity may
be typically in a range of 20 to 10000 mJ/cm.sup.2 and preferably
in a range of 100 to 3000 mJ/cm.sup.2.
Moreover, the heat treatment or light irradiation may be performed
in stages. Further, from the viewpoint of controlling the
temperature, the temperature of a roll that comes into contact with
the film may be controlled.
Hereinafter, preferred embodiments (1 and 2) of a composition for
forming a hard coat layer used to form a hard coat layer will be
described below.
[Composition (1) for Forming Hard Coat Layer]
In the present invention, a hard coat layer can be formed on the
conductive layer by applying, drying, and curing a compound having
an unsaturated double bond, a polymerization initiator, if
necessary, light-transmitting particles, a fluorine-containing
compound, or a silicone-based compound, or a composition containing
a solvent directly or through another layer.
Hereinafter, each component included in the composition (1) for
forming a hard coat layer will be described.
(Compound Having Unsaturated Double Bond)
The composition for forming a hard coat layer may contain a
compound having an unsaturated double bond. The compound having an
unsaturated double bond may function as a binder and it is
preferable that the compound is a polyfunctional monomer having two
or more polymerizable unsaturated groups. The polyfunctional
monomer having two or more polymerizable unsaturated groups may
function as a curing agent and is capable of improving the strength
of a coated film and abrasion resistance. The number of
polymerizable unsaturated groups is more preferably three or more.
These monomers can be used in combination of a monofunctional or
difunctional monomer with a tri- or higher functional monomer.
Examples of the compound having an unsaturated double bond include
compounds having a polymerizable functional group such as a
(meth)acryloyl group, a vinyl group, a styryl group, or an allyl
group. Among these, a (meth)acryloyl group and C(O)OCH.dbd.CH.sub.2
are preferable. It is particularly preferable that a compound
containing three or more (meth)acryloyl groups in a molecule,
described below, is used. In addition, the term "(meth)acryloyl
group" indicates an acryloyl group or a methacryloyl group.
Similarly, the term "(meth)acrylic acid" described below indicates
acrylic acid or methacrylic acid and the term "(meth)acrylate"
indicates acrylate or methacrylate.
Specific examples of the compound having a polymerizable
unsaturated bond include (meth)acrylic acid diesters of alkylene
glycol, (meth)acrylic acid diesters of polyoxyalkylene glycol,
(meth)acrylic acid diesters of polyhydric alcohol, (meth)acrylic
acid diesters of an ethylene oxide adduct or a propylene oxide
adduct, epoxy (meth)acrylates, urethane (meth)acrylates, and
polyester (meth)acrylates.
Among these, esters of polyhydric alcohol and (meth)acrylic acid
are preferable. Examples thereof include 1,4-butanediol
di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol
(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene
glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate,
pentaerythritol tri(meth)acrylate, trimethylol propane
tri(meth)acrylate, EO-modified trimethylol propane
tri(meth)acrylate, PO-modified trimethylol propane
tri(meth)acrylate, EO-modified phosphoric acid tri(meth)acrylate,
trimethylolethane tri(meth)acrylate, ditrimethylolpropane
tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate, dipentaerythritol
hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate,
polyurethane polyacrylate, polyester polyacrylate, and
caprolactone-modified tris(acryloxyethyl)isocyanurate.
Polyfunctional acrylate-based compounds having a (meth)acryloyl
group are commercially available and examples thereof include NK
ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) and
KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.).
Polyfunctional monomers are described in paragraphs [0114] to
[0122] of JP2009-98658A and the same applies to the present
invention.
From the viewpoints of adhesiveness to the conductive layer, low
curling, and fixing properties of fluorine-containing compounds or
silicone-based compounds described below, it is preferable that the
compound having an unsaturated double bond is a compound having a
hydrogen-bonding substituent. The hydrogen-bonding substituent
indicates a substituent obtained by covalently bonding an atom
having high electronegativity such as nitrogen, oxygen, sulfur, or
halogen to a hydrogen bond, and specific examples thereof include
OH--, SH--, NH--, CHO--, and CHN--. Among these, urethane
(meth)acrylates or (meth)acrylates having a hydroxyl group are
preferable. Further, commercially available polyfunctional acrylate
having a (meth)acryloyl group can be used and examples thereof
include NK OLIGO U4HA, NK ESTER A-TMM-3 (both manufactured by
Shin-Nakamura Chemical Co., Ltd.), and KAYARAD PET-30 (manufactured
by Nippon Kayaku Co., Ltd.).
From the viewpoint of imparting a sufficient degree of
polymerization to provide hardness, the content of the compound
having an unsaturated double bond in the composition for forming a
hard coat layer is preferably 50% by mass or greater, more
preferably in a range of 60% to 99% by mass, still more preferably
in a range of 70% to 99% by mass, and particularly preferably in a
range of 80% to 99% by mass with respect to the total solid content
obtained by removing inorganic components from the composition for
forming a hard coat layer.
It is preferable that a compound having cyclic aliphatic
hydrocarbon and an unsaturated double bond in a molecule is used
for the composition for forming a hard coat layer. When such a
compound is used, low moisture permeability can be provided for a
hard coat layer. In order to improve hard coat properties, it is
more preferable to use a compound having two or more cyclic
aliphatic hydrocarbons and unsaturated double bonds in a
molecule.
In a case where the composition for forming a hard coat layer
contains a compound having cyclic aliphatic hydrocarbon and an
unsaturated double bond in a molecule, the content of the compound,
having cyclic aliphatic hydrocarbon and an unsaturated double bond
in a molecule, in a compound having an unsaturated double bond in
the composition for forming a hard coat layer is preferably in a
range of 1% to 90% by mass, more preferably in a range of 2% to 80%
by mass, and still more preferably in a range of 5% to 70% by
mass.
In a case where the composition for forming a hard coat layer
contains a compound having cyclic aliphatic hydrocarbon and an
unsaturated double bond in a molecule, it is preferable that the
composition further contains penta- or higher functional
(meth)acrylate.
In a case where the composition for forming a hard coat layer
contains penta- or higher functional (meth)acrylate, the content of
the penta- or higher functional (meth)acrylate in the compound
having an unsaturated double bond in the composition for forming a
hard coat layer is preferably in a range of 1% to 70% by mass, more
preferably in a range of 2% to 60% by mass, and particularly
preferably in a range of 5% to 50% by mass.
(Light-Transmitting Particles)
When a hard coat layer contains light-transmitting particles, it is
possible to provide an uneven shape or inside haze for the surface
of the hard coat layer.
Examples of light-transmitting particles which can be used for the
hard coat layer include polymethyl methacrylate particles
(refractive index of 1.49), crosslinked poly(acryl-styrene)
copolymer particles (refractive index of 1.54), melamine resin
particles (refractive index of 1.57), polycarbonate particles
(refractive index of 1.57), polystyrene particles (refractive index
of 1.60), crosslinked polystyrene particle (refractive index of
1.61), polyvinyl chloride particles (refractive index of 1.60),
benzoguanamine-melamine formaldehyde particles (refractive index of
1.68), silica particles (refractive index of 1.46), alumina
particles (refractive index of 1.63), zirconia particles, titanium
particles, and particles having hallows or pores.
Among these, crosslinked ((meth)acrylate) particles, crosslinked
poly(acryl-styrene) particles are preferably used, and the
unevenness, surface haze, inside haze, and total haze suitable for
the hard coat layer can be achieved by adjusting the refractive
index of a binder in accordance with the refractive index of
respective light-transmitting particles selected from these
particles. The refractive index of the binder (light-transmitting
resin) is preferably in a range of 1.45 to 1.70 and more preferably
in a range of 1.48 to 1.65.
Further, a difference in refractive index between the
light-transmitting particles and the binder in the hard coat layer
("refractive index of light-transmitting particles"-"refractive
index of hard coat layer from which light-transmitting particles
are removed") is, as an absolute value, preferably less than 0.05,
more preferably in a range of 0.001 to 0.030, and still more
preferably in a range of 0.001 to 0.020. It is preferable that the
difference in refractive index between the light-transmitting
particles and the binder in the hard coat layer is set to be less
than 0.05 because the refracting angle of light due to
light-transmitting particles becomes small, scattered light does
not spread to have a wide angle, and a deterioration action does
not exist.
In order to obtain the above-described difference in refractive
index between the particles and the binder, the refractive index of
the light-transmitting particles or the refractive index of the
binder may be adjusted.
According to a preferred first embodiment, it is preferable to use
a combination of light-transmitting particles formed of a binder
(the refractive index after curing is in a range of 1.50 to 1.53)
having a tri- or higher functional (meth)acrylate monomer as a main
component and a crosslinked poly(meth)acrylate-styrene copolymer
having 50% to 100% by mass of acryl. The difference in refractive
index between the light-transmitting particles and the binder is
easily set to be less than 0.05 by adjusting the compositional
ratio of an acryl component having a low refractive index and a
styrene component having a high refractive index. The mass ratio
between the acrylic component and the styrene component is
preferably in a range of 50:50 to 100:0, more preferably in a range
of 60:40 to 100:0, and most preferably in a range of 65:35 to
90:10. The refractive index of light-transmitting particles formed
of a crosslinked poly(meth)acrylate-styrene copolymer is preferably
in a range of 1.49 to 1.55, more preferably in a range of 1.50 to
1.54, and most preferably in a range of 1.51 to 1.53.
According to a preferred second embodiment, the refractive index of
a binder formed of monomers and inorganic fine particles is
adjusted and the difference in refractive index between the binder
and light-transmitting particles of the related art is adjusted by
combining inorganic fine particles having an average particle size
of 1 to 100 nm with a binder having a tri- or higher functional
(meth)acrylate monomer as a main component. Examples of inorganic
particles include an oxide of at least one metal selected from
silicon, zirconium, titanium, aluminum, indium, zinc, tin, and
antimony and specific examples thereof include SiO.sub.2,
ZrO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, In.sub.2O.sub.3, ZnO,
SnO.sub.2, Sb.sub.2O.sub.3, and ITO. Among these, SiO.sub.2,
ZrO.sub.2, or Al.sub.2O.sub.3 is preferable. These inorganic
particles can be mixed in a range of 1% to 90% by mass and
preferably in a range of 5% to 65% by mass with respect to the
total amount of monomers.
Here, the refractive index of the hard coat layer from which
light-transmitting particles are removed can be quantitatively
evaluated by directly measuring the value using an Abbe
refractometer or measuring the spectral reflection spectrum or
spectral ellipsometry. The refractive index of the
light-transmitting particles is obtained by dispersing the
equivalent amount of light-transmitting particles in a solvent
whose refractive index is changed by changing the mixing ratio of
two kinds of solvents having different refractive index to measure
the turbidity and measuring the refractive index of the solvent at
the time when the turbidity becomes minimum using a Abbe
refractometer.
The average particle diameter of light-transmitting particles is
preferably in a range of 1.0 to 12 .mu.m, more preferably in a
range of 3.0 to 12 .mu.m, and still more preferably in a range of
4.0 to 10.0 .mu.m, and most preferably in a range of 4.5 to 8
.mu.m. When the difference in refractive index and the grain size
are set to be in the above-described range, the scattering angle
distribution of light does not spread to a wide angle and blurred
characters and contrast deterioration of a display are unlikely to
occur. From the viewpoints that the film thickness of a layer to be
added does not need to be increased and a problem of curling or an
increase in cost is unlikely to occur, the average particle
diameter thereof is preferably 12 .mu.m or less. It is preferable
that the average particle diameter thereof is in the
above-described range from the viewpoints that the coating amount
at the time of application is suppressed, the coated surface is
rapidly dried, and planar defects such as uneven drying are
unlikely to be generated.
Any measurement method can be used as a method of measuring the
average particle diameter of light-transmitting particles as long
as the method is for measuring the average particle diameter of
particles, but, preferably, the average particle diameter thereof
can be obtained by observing particles using a transmission
electron microscope (magnification of 500000 to 2000000 times),
observing 100 particles, and calculating the average value.
The shape of the light-transmitting particles is not particularly
limited, but light-transmitting particles having different shapes
such as deformed particles (for example, non-spherical particles)
may be used in combination in place of spherical particles.
Particularly when the short axis of non-spherical particles is
aligned to the normal direction of the hard coat layer, particles
having small particle diameters compared to the spherical particles
can be used.
It is preferable light-transmitting particles are blended into the
hard coat layer such that the content thereof is in a range of 0.1%
to 40% by mass with respect to the total solid content of the hard
coat layer. The content thereof is more preferably in a range of 1%
to 30% by mass and still more preferably in a range of 1% to 20% by
mass. When the blending ratio of light-transmitting particles is
set to be in the above-described range, the inside haze can be
controlled to be in the preferable range.
Moreover, the amount of light-transmitting particles to be applied
is preferably in a range of 10 to 2500 mg/m.sup.2, more preferably
in a range of 30 to 2000 mg/m.sup.2, and still more preferably in a
range of 100 to 1500 mg/m.sup.2.
Examples of the method of producing light-transmitting particles
include a suspension polymerization method, an emulsion
polymerization method, a soap-free emulsion polymerization method,
a dispersion polymerization method, and a seed polymerization
method, and light-transmitting particles may be produced any of
these methods. These production methods can be referred to methods
described in, for example, "Experimental Method of Polymer
Synthesis" (co-edited by Takayuki Otsu and Kinoshita Masayoshi,
published by KAGAKUDOJIN), p. 130, 146, and 147; "Synthetic
Polymer" Vol. 1, p. 246 to 290; "Synthetic Polymer" Vol. 3, p. 1 to
108; JP2543503B; JP3508304B; JP2746275B; JP3521560B; JP3580320B;
JP1998-1561A (JP-H10-1561A), JP1995-2908A (JP-H07-2908A),
JP1993-297506A (JP-H05-297506A), and JP2002-145919A.
From the viewpoints of controlling the haze value and diffusibility
and evenness of the coated surface state, monodisperse particles
are preferable as the particle size distribution of
light-transmitting particles. A CV value representing uniformity of
particle diameters is preferably 15% or less, more preferably 13%
or less, and still more preferably 10% or less. Further, in a case
where a particle having a particle diameter larger than the average
particle diameter by 20% or greater is defined as a coarse
particle, the percentage of the coarse particles is preferably 1%
or less, more preferably 0.1% or less, and still more preferably
0.01% or less. Particles having such particle size distribution are
obtained by classification as useful means after preparation or a
synthetic reaction. When the number of times of classifications is
increased and the degree thereof is made to be high, particles
having desired distribution can be obtained.
It is preferable that an air classification method, a centrifugal
classification method, a filtration classification method, or an
electrostatic classification method is used for the above-described
classification.
(Photopolymerization Initiator)
It is preferable that the composition for forming a hard coat layer
contains a photopolymerization initiator.
From the viewpoints that the amount of a photopolymerization
initiator is sufficiently large enough for polymerizing a
polymerizable compound contained in the composition for forming a
hard coat layer and the amount thereof is set to be sufficiently
low such that the start point is not extremely increased, the
content of the photopolymerization initiator in the composition for
forming a hard coat layer is preferably in a range of 0.5% to 8% by
mass and more preferably in a range of 1% to 5% by mass with
respect to the total solid content in the composition for forming a
hard coat layer.
(Ultraviolet Absorbing Agent)
The conductive film is used for a member or the like of a display
device provided with a touch panel. From the viewpoint of
preventing deterioration of liquid crystals or the like,
ultraviolet absorbing properties can be provided for the conductive
film by allowing the hard coat layer to contain an ultraviolet
absorbing agent within the range that does not inhibit UV
(ultraviolet rays) curing.
(Solvent)
The composition for forming a hard coat layer may contain a
solvent. As the solvent, various solvents can be used in
consideration of solubility of a monomer, dispersibility of
light-transmitting particles, and drying properties during
application. Examples of organic solvents include dibutyl ether,
dimethoxy ethane, diethoxy ethane, propylene oxide, 1,4-dioxane,
1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole,
dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate,
acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl
ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl
cyclohexanone, ethyl formate, propyl formate, pentyl formate,
methyl acetate, ethyl acetate, propyl acetate, methyl propionate,
ethyl propionate, .gamma.-butyrolactone, methyl 2-methoxy acetate,
methyl 2-ethoxy acetate, ethyl 2-ethoxy acetate, ethyl 2-ethoxy
propionate, 2-methoxy ethanol, 2-propoxy ethanol, 2-buthoxy
ethanol, 1,2-diacetoxy acetone, acetyl acetone, diacetone alcohol,
methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethyl
alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol,
isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone,
2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene
glycol isopropyl ether, ethylene glycol butyl ether, propylene
glycol methyl ether, ethyl carbitol, butyl carbitol, hexane,
heptane, octane, cyclohexane, methyl cyclohexane, ethyl
cyclohexane, benzene, toluene, and xylene, and organic solvents can
be used alone or in combination of two or more kinds thereof.
A solvent is used such that the concentration of the solid content
in the composition for forming a hard coat layer is set to be
preferably in a range of 20% to 80% by mass, more preferably in a
range of 30% to 75% by mass, and still more preferably in a range
of 40% to 70% by mass.
[Composition (2) for Forming Hard Coat Layer]
Next, a composition for forming an (antistatic) hard coat layer
used for an antistatic antireflection film will be described.
Hereinafter, various components contained in the composition (2)
for forming a hard coat layer will be described in detail.
(Compound Having Quaternary Ammonium Base)
The composition for forming a hard coat layer contains a compound
having a quaternary ammonium base.
As the compound having a quaternary ammonium base, both of a low
molecular type compound and a high molecular type compound can be
used, but a high molecular type cationic compound is more
preferably used from the viewpoint that the high molecular type
cationic compound does not have a variation in antistatic
properties due to bleed out.
The high molecular type cationic compound having a quaternary
ammonium base can be selected from known compounds for use, but a
quaternary ammonium base-containing polymer is preferable and a
polymer having at least one structural unit represented by any of
the following Formulae (I) to (III) is preferable, from the
viewpoint of excellent ion conductivity.
##STR00001##
In Formula (I), R.sub.1 represents a hydrogen atom, an alkyl group,
a halogen atom, or CH.sub.2COO.sup.-M.sup.+. Y represents a
hydrogen atom or COO-M+. M+ represents a proton or a cation. L
represents --CONH--, --COO--, --CO--, or --O--. J represents an
alkylene group, an arylene group, or a group formed by combining
these. Q represents a group selected from the following group
A.
##STR00002##
In the formulae, R.sub.2, R.sub.2', and R.sub.2'' each
independently represent an alkyl group. J represents an alkylene
group, an arylene group, or a group formed by combining these.
X.sup.- represents an anion. p and q each independently represent 0
or 1.
##STR00003##
In Formula (II), R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each
independently represent an alkyl group. Further, R.sub.3 and
R.sub.4, and R.sub.5 and R.sub.6 may be bonded to each other to
respectively form a nitrogen-containing heterocycle.
A and B in Formula (II) and D in Formula (III) each independently
represent an alkylene group, an arylene group, an alkenylene group,
an arylene-alkylene group, --R.sub.7COR.sub.8--,
--R.sub.9COOR.sub.10OCOR.sub.11--,
--R.sub.12OCR.sub.13COOR.sub.14--, --R.sub.15--(OR.sub.16)m-,
R.sub.17CONHR.sub.18NHCOR.sub.19--,
--R.sub.20OCONHR.sub.21NHCOR.sub.22--, or
--R.sub.23NHCONHR.sub.24NHCONHR.sub.25--.
E in Formula (III) represents a single bond, an alkylene group, an
arylene group, an alkenylene group, an arylene-alkylene group,
--R.sub.7COR.sub.8--, --R.sub.9COOR.sub.10OCOR.sub.11--,
--R.sub.12OCR.sub.13COOR.sub.14--, --R.sub.15--(OR.sub.16)m-,
R.sub.17CONHR.sub.18NHCOR.sub.19--,
--R.sub.20OCONHR.sub.21NHCOR.sub.22--,
--R.sub.23NHCONHR.sub.24NHCONHR.sub.25--, or --NHCOR.sub.26CONH--.
R.sub.7, R.sub.8, R.sub.9, R.sub.11, R.sub.12, R.sub.14, R.sub.15,
R.sub.16, R.sub.17, R.sub.19, R.sub.20, R.sub.22, R.sub.23,
R.sub.25, and R.sub.26 represent an alkylene group. R.sub.10,
R.sub.13, R.sub.18, R.sub.21, and R.sub.24 each independently
represent a linking group selected from an alkylene group, an
alkenylene group, an arylene group, an arylene-alkylene group, and
an alkylene-arylene group. m represents a positive integer of 1 to
4.
X- represents an anion.
Z.sub.1 and Z.sub.2 represent a nonmetallic atomic group required
for forming a 5- or 6-membered ring together with a --N.dbd.C--
group and may be linked to E in the form of a quaternary salt which
becomes .ident.N.sup.+[X.sup.-]--.
n represents an integer of 5 to 300.
Groups of Formulae (I) to (III) will be described.
Examples of a halogen atom include a chlorine atom and a bromine
atom. Among these, a chlorine atom is preferable.
As an alkyl group, a branched or linear alkyl group having 1 to 4
carbon atoms is preferable and a methyl group, an ethyl group, or a
propyl group is more preferable.
As an alkylene group, an alkylene group having 1 to 12 carbon atoms
is preferable and a methylene group, an ethylene group, or a
propylene group is more preferable, and an ethylene group is
particularly preferable.
As an arylene group, an arylene group having 6 to 15 carbon atoms
is preferable, a phenylene group, a diphenylene group, a phenyl
dimethylene group, or a naphthylene group is more preferable and a
phenyl methylene group is particularly preferable. These groups may
include a substituent.
As an alkenylene group, an alkenylene group having 2 to 10 carbon
atoms is preferable. As arylene-alkylene group, an arylene-alkylene
group having 6 to 12 carbon atoms is preferable. These groups may
include a substituent.
Examples of the substituent which may be substituted with each
group include a methyl group, an ethyl group, and a propyl
group.
In Formula (I), it is preferable that R1 represents a hydrogen atom
or a methyl group.
It is preferable that Y represents a hydrogen atom.
It is preferable that L represents --COO--.
It is preferable that J represents a phenylmethylene group, a
methylene group, an ethylene group, or a propylene group.
Q represents a group represented by the following Formula (VI) and
R.sub.2, R.sub.2', and R.sub.2'' each represent a methyl group.
X-- represents a halogen ion, a sulfonate anion, or a carboxylate
anion. Among these, a halogen ion is preferable and a chlorine ion
is more preferable.
It is preferable that p and q represent 0 or 1 and more preferable
that p and q represent 1.
##STR00004##
In Formula (II), R.sub.3, R.sub.4, R.sub.5, and R.sub.6 represent
preferably a substituted or unsubstituted alkyl group having 1 to 4
carbon atoms, more preferably a methyl group or an ethyl group, and
particularly preferably a methyl group.
A and B in Formula (II) and D in Formula (III) each independently
represent preferably a substituted or unsubstituted alkylene group
having 2 to 10 carbon atoms, an arylene group, an alkenylene group,
or an arylene-alkylene group and more preferably a
phenyldimethylene group.
X-- represents a halogen ion, a sulfonate anion, or a carboxylate
anion. Among these, a halogen ion is preferable and a chlorine ion
is more preferable.
It is preferable that E represents a single bond, an alkylene
group, an arylene group, an alkenylene group, or an
arylene-alkylene group.
As the 5- or 6-membered ring formed by Z.sub.1 and Z.sub.2 together
with a --N.dbd.C-- group, a diazoniabicyclooctane ring or the like
may be exemplified.
Hereinafter, specific examples of the compound having a structural
unit represented by any of Formulae (I) to (III) will be described,
but the present invention is not limited thereto. In the subscripts
(m, x, y, r, and actual numerical values) of the following specific
examples, m represents the number of repeating units of each unit
and x, y, and r represent the molar ratio of each unit.
##STR00005## ##STR00006## ##STR00007##
The conductive compounds exemplified in the above may be used alone
or in combination of two or more compounds. Further, an antistatic
compound having a polymerizable group in a molecule of an
antistatic agent is more preferable because scratch resistance
(film hardness) of an antistatic layer can be also improved.
As the compound having a quaternary ammonium base, commercially
available products can be used. Examples thereof include "LIGHT
ESTER DQ-100" (trade name, manufactured by KYOEISHA CHEMICAL Co.,
Ltd.), "LIODURAS LAS-1211" (trade name, manufactured by TOYO INK
CO., LTD.), "SHIKOU UV-AS-102" (trade name, manufactured by Nippon
Synthetic Chemical Industry Co., Ltd.), and "NK OLIGO U-601 and
201" (manufactured by Shin-Nakamura Chemical Co., Ltd.).
A quaternary ammonium base-containing polymer may include a
structural unit (repeating unit) other than the structural units
(ionic structural units) represented by the above-described
Formulae (I) to (III). When a compound having a quaternary ammonium
base includes a structural unit other than ionic structural units,
solubility in a solvent during preparation of a composition and
compatibility with a compound having an unsaturated double bond or
a photopolymerization initiator can be improved.
The polymerizable compound used to introduce a structural unit
other than structural units represented by the above-described
Formulae (I) to (III) is not particularly limited, and examples
thereof include polymerizable compounds selected from a compound
having an alkylene oxide chain such as polyethylene glycol
mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,
polybutylene glycol mono(meth)acrylate, poly(ethylene
glycol-propylene glycol) mono(meth)acrylate, poly(ethylene
glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene
glycol-tetramethylene glycol) mono(meth)acrylate, polyethylene
glycol mono(meth)acrylate monomethyl ether, polyethylene glycol
mono(meth)acrylate monobutyl ether, polyethylene glycol
mono(meth)acrylate monooctyl ether, polyethylene glycol
mono(meth)acrylate monobenzyl ether, polyethylene glycol
mono(meth)acrylate monophenyl ether, polyethylene glycol
mono(meth)acrylate monodecyl ether, polyethylene glycol
mono(meth)acrylate monododecyl ether, polyethylene glycol
mono(meth)acrylate monotetradecyl ether, polyethylene glycol
mono(meth)acrylate monohexadecyl ether, polyethylene glycol
mono(meth)acrylate monooctadecyl ether, poly(ethylene
glycol-propylene glycol) mono(meth)acrylate octyl ether,
poly(ethylene glycol-propylene glycol) mono(meth)acrylate octadecyl
ether, or poly(ethylene glycol-propylene glycol) mono(meth)acrylate
nonyl phenyl ether; alkyl (meth)acrylate such as methyl
(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl
(meth)acrylate, or octadecyl (meth)acrylate; hydroxyalkyl
(meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, or hydroxybutyl (meth)acrylate; various
(meth)acrylates such as benzyl (meth)acrylate, cyclohexyl
(meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl
(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl
(meth)acrylate, ethylcarbitol (meth)acrylate, butoxyethyl
(meth)acrylate, cyanoethyl (meth)acrylate, and glycidyl
(meth)acrylate; styrene; and methylstyrene; and combinations of
these.
From the viewpoints that the amount of the compound having a
quaternary ammonium base in the composition for forming a hard coat
layer is sufficient enough to provide antistatic properties and the
film hardness is unlikely to be impaired, the content thereof is
preferably in a range of 1% to 30% by mass, more preferably in a
range of 3% to 20% by mass, and still more preferably in a range of
5% to 15% by mass with respect to the total solid content in the
composition for forming a hard coat layer.
(Compound Having Unsaturated Double Bond)
The composition for forming a hard coat layer may contain a
compound having an unsaturated double bond. The compound having an
unsaturated double bond has the same definition as the compound
described in the above-described section of "Composition (1) for
forming hard coat layer".
From the viewpoint of imparting a polymerization rate sufficiently
to provide the hardness or the like, the content of the compound
having an unsaturated double bond in the composition for forming a
hard coat layer is preferably in a range of 40% to 98% by mass and
more preferably in a range of 60% to 95% by mass with respect to
the total solid content in the composition for forming a hard coat
layer.
(Photopolymerization Initiator)
The composition for forming a hard coat layer may contain a
photopolymerization initiator.
Examples of the photopolymerization initiator include
acetophenones, benzoins, benzophenones, phosphine oxides, ketals,
anthraquinones, thioxanthones, azo compounds, peroxides,
2,3-dialkyldione compounds, disulfide compounds, fluoroamine
compounds, aromatic sulfoniums, lophine dimers, onium salts, borate
salts, active esters, active halogens, inorganic complexes, and
coumarins. The specific examples, preferred embodiments, and
commercially available products of the photopolymerization
initiator are the same as those described in paragraphs [0133] to
[0151] of JP2009-098658A, and those can be also suitably used in
the present invention.
Various examples thereof are also described in "Latest UV Curing
Technology" {Technical Information institute Co., Ltd.} (1991), p.
159 and "UV Curing System" written by Kiyoshi Kato (1989, published
by Sogo Gijutsu Center Co., Ltd.), p. 65 to 148 and the examples
can be used in the present invention.
From the viewpoints that the amount of a photopolymerization
initiator is sufficiently large enough to polymerize a
polymerizable compound contained in the composition for forming a
hard coat layer and the amount thereof is set to be sufficiently
low such that the start point is not extremely increased, the
content of the photopolymerization initiator in the composition for
forming a hard coat layer is preferably in a range of 0.5% to 8% by
mass and more preferably in a range of 1% to 5% by mass with
respect to the total solid content in the composition for forming a
hard coat layer.
(Solvent)
The composition for forming a hard coat layer may contain various
organic solvents.
From the viewpoint of obtaining compatibility with an
ion-conductive compound, it is preferable that the composition of
the present invention contains a hydrophilic solvent. Examples of
the hydrophilic solvent include alcohol-based solvents,
carbonate-based solvents, and ester-based solvents. Specific
examples thereof include methanol, ethanol, isopropanol, n-butyl
alcohol, cyclohexyl alcohol, 2-ethyl-1-hexanol, 2-methyl-1-hexanol,
2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, diacetone
alcohol, dimethyl carbonate, diethyl carbonate, diisopropyl
carbonate, methyl ethyl carbonate, methyl n-propyl carbonate, ethyl
formate, propyl formate, pentyl formate, methyl acetate, ethyl
acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl
2-ethoxy propionate, methyl acetoacetate, ethyl acetoacetate,
methyl 2-methoxy acetate, methyl 2-ethoxy acetate, ethyl 2-ethoxy
acetate, acetone, 1,2-diacetoxy acetone, and acetyl acetone, and
these solvents can be used alone or in combination of two or more
kinds thereof.
Further, solvents other than the above-described solvents may be
used. Examples thereof include ether-based solvents, ketone-based
solvents, aliphatic hydrocarbon-based solvents, and aromatic
hydrocarbon-based solvents. Specific examples thereof include
dibutyl ether, dimethoxy ethane, diethoxy ethane, propylene oxide,
1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran,
anisole, phenetole, methyl ethyl ketone (MEK), diethyl ketone,
dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone,
methyl cyclohexanone, methyl isobutyl ketone, 2-octane,
2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene
glycol isopropyl ether, ethylene glycol butyl ether, propylene
glycol methyl ether, ethyl carbitol, butyl carbitol, hexane,
heptane, octane, cyclohexane, methyl cyclohexane, ethyl
cyclohexane, benzene, toluene, and xylene, and these solvents can
be used alone or in combination of two or more kinds thereof.
A solvent is used such that the concentration of the solid content
in the composition for forming a hard coat layer is preferably in a
range of 20% to 80% by mass, more preferably in a range of 30% to
75% by mass, and most preferably in a range of 40% to 70% by
mass.
(Surfactant)
Various surfactants may be suitably used for the composition for
forming a hard coat layer. Typically, a surfactant suppresses film
thickness irregularity caused by uneven drying due to local
distribution of dry air and improves surface unevenness of an
antistatic layer or cissing a coated product. In addition,
preferably, excellent conductivity can be more stably expressed in
some cases by improving the dispersibility of an antistatic
compound.
As a surfactant, specifically, a fluorine-based surfactant or a
silicone-based surfactant is preferable. Further, it is preferable
that a surfactant is an oligomer or a polymer rather than a
low-molecular weight compound.
When a surfactant is added, since the surfactant is rapidly moved
to the surface of a coated liquid film and unevenly distributed and
the surfactant is unevenly distributed on the surface as it is
after the film is dried, the surface energy of the hard coat layer
to which the surfactant is added is decreased due to the
surfactant. From the viewpoint of preventing film thickness
irregularity, cissing, and unevenness of the hard coat layer, it is
preferable that the surface energy of the film is low.
Particularly from the viewpoint of preventing point defects caused
by cissing and unevenness, a fluoroaliphatic group-containing
copolymer including a repeating unit derived from a monomer
containing a fluoroaliphatic group represented by the following
Formula (F1) and a repeating unit derived from a monomer which does
not contain a fluoroaliphatic group represented by the following
Formula (F2) is preferable as the fluorine-based surfactant.
##STR00008##
(In the formula, R.sup.0 represents a hydrogen atom, a halogen
atom, or a methyl group. L represents a divalent linking group. n
represents an integer of 1 to 18.)
##STR00009##
(In the formula, R.sup.1 represents a hydrogen atom, a halogen
atom, or a methyl group. L.sup.1 represents a divalent linking
group. Y represents a linear, branched, or cyclic alkyl group which
may have a substituent and has 1 to 20 carbon atoms or an aromatic
group which may have a substituent.)
It is preferable that a monomer containing a fluoroaliphatic group
represented by Formula (F1) is a monomer containing a
fluoroaliphatic group represented by the following Formula
(F1-1).
##STR00010##
(In the formula, R.sup.1 represents a hydrogen atom, a halogen
atom, or a methyl group. X represents an oxygen atom, a sulfur
atom, or --N(R.sup.2)--. m represents an integer of 1 to 6. n
represents an integer of 1 to 18. R.sup.2 represents a hydrogen
atom or an alkyl group which may have a substituent and has 1 to 8
carbon atoms.)
Preferred embodiments and specific examples of the fluoroaliphatic
group-containing copolymer are described in paragraphs [0023] to
[0080] of JP2007-102206A and the same applies to the present
invention.
Preferred examples of the silicone-based surfactant include
surfactants which include plural dimethylsilyloxy units as
repeating units and have substituents at the terminal and/or side
chain of the compound chain. The compound chain having
dimethylsilyloxy as a repeating unit may include a structural unit
other than dimethylsilyloxy. The substituents may be the same as or
different from each other and it is preferable that a plurality of
substituents are present. Preferred examples of the substituents
include groups having a polyether group, an alkyl group, an aryl
group, an aryloxy group, a cinnamoyl group, an oxetanyl group, a
fluoroalkyl group, or a polyoxyalkylene group.
The molecular weight is not particularly limited, but is preferably
100000 or less and more preferably 50000 or less, particularly
preferably in a range of 1000 to 30000, and most preferably in a
range of 1000 to 20000.
Preferred examples of the silicone-based compound include
"X-22-174DX", "X-22-2426", "X22-164C", "X-22-176D" (all trade
names, manufactured by Shin-Etsu Chemical Co., Ltd.); "FM-7725",
"FM-5521", "FM-6621", (all trade names, manufactured by CHISSO
CORPORATION); "DMS-U22", "RMS-033" (all trade names, manufactured
by Gelest, Inc.); "SH200", "DC11PA", "ST80PA, "L7604", "FZ-2105",
"L-7604", "Y-7006", "SS-2801" (all trade names, manufactured by Dow
Corning Toray Co., Ltd.); and "TSF400" (trade name, manufactured by
Momentive Performance Materials Inc.), but the examples are not
limited to these.
The content of the surfactant is preferably in a range of 0.01% to
0.5% by mass and more preferably in a range of 0.01% to 0.3% by
mass with respect to the total solid content of the composition for
forming a hard coat layer.
Moreover, a photosensitive composition described in JP2012-78528A
may be used as the composition for forming a hard coat layer in
place of the composition (1) for forming a hard coat layer and the
composition (2) for forming a hard coat layer described above.
<Protective Film (Polarizer Protective Film)>
A protective film is arbitrarily disposed on the surface of the
polarizer on the opposite side to the conductive layer side and has
a function of protecting the polarizer.
As the protective film, a known transparent support can be used.
Examples of the material that forms a transparent support include a
cellulose acylate resin represented by triacetyl cellulose, a
cycloolefine resin (ZEONEX and ZEONOR manufactured by ZEON
CORPORATION or ARTON manufactured by JSR Corporation), a (meth)
acrylic resin, and a polyester resin.
The thickness of the protective film is not particularly limited,
but is preferably 40 .mu.m or less and more preferably 25 .mu.m or
less from the viewpoint that the thickness can be reduced.
<.lamda./4 Plate>
A .lamda./4 plate is an optional layer disposed between the
polarizer and the conductive film. When the .lamda./4 plate is
disposed, a circularly polarizing plate can be formed with the
polarizer and the .lamda./4 plate. The circularly polarizing plate
can be used for preventing reflection of external light.
The .lamda./4 plate (plate having the .lamda./4 function) is a
plate having a function of converting linearly polarized light
having a specific wavelength into circularly polarized light
(alternatively, circularly polarized light into linearly polarized
light). More specifically, the .lamda./4 plate is a plate in which
the in-plane retardation value at a predetermined wavelength of
.lamda. nm is .lamda./4 (or odd times this value).
An in-plane retardation value (Re (550)) at a wavelength of 550 nm
in the .lamda./4 plate may have an error of approximately 25 nm, is
preferably in a range of 110 to 160 nm, more preferably in a range
of 120 to 150 nm, and still more preferably in a range of 130 to
145 nm based on the ideal value (137.5 nm).
In a case where the polarizer and the .lamda./4 plate function as a
circularly polarized light plate, the angle .theta. formed by an
absorption axis of the polarizer and the in-plane slow axis of the
.lamda./4 plate is preferably in a range of 45.+-.100 when a
.lamda./4 plate having a single-layer structure is used. In other
words, the angle .theta. is preferably in a range of 35.degree. to
55.degree..
Moreover, the angle indicates an angle formed by the absorption
axis of the polarizer and the in-plane slow axis of the .lamda./4
plate when seen from the normal direction of the surface of the
polarizer.
The .lamda./4 plate may have a multilayer structure. As an example
of the multilayer structure, a broadband .lamda./4 plate formed by
laminating a .lamda./2 plate and a .lamda./4 plate on each other
may be exemplified. For example, in a case where a polarizer and a
broadband .lamda./4 plate (including a .lamda./2 plate and a
.lamda./4 plate from the polarizer side) are laminated on each
other, the angle formed by a transmission axis of the polarizer and
an in-plane slow axis of the .lamda./2 plate is preferably in a
range of 15.+-.10.degree. and the angle formed by the transmission
axis of the polarizer and an in-plane slow axis of the .lamda./4
plate is preferably in a range of 75.+-.10.degree..
A material constituting the .lamda./4 plate is not particularly
limited as long as the material shows the above-described
characteristics, and examples thereof include a material containing
a liquid crystal compound (for example, a homogeneously aligned
optically anisotropic layer including a liquid crystal compound)
and a polymer film. Among these, a material containing a liquid
crystal compound is preferable from the viewpoint that the
above-described characteristic are easily controlled. More
specifically, it is preferable that the .lamda./4 plate is a layer
formed by fixing a liquid crystal compound (a rod-like liquid
crystal compound or a discotic liquid crystal compound) including a
polymerizable group through polymerization or the like. In this
case, the .lamda./4 plate does not need to exhibit liquid
crystallinity after becoming a layer.
<Conductive Film and Applications Thereof>
The conductive film of the present invention includes at least the
polarizer and the conductive layer which is disposed on the
polarizer and contains fullerene functionalized carbon
nanotubes.
The sheet resistance value of the conductive film is not
particularly limited, but is preferably in a range of 10 to
150.OMEGA./.quadrature. and more preferably in a range of 10 to
100.OMEGA./.quadrature., from the viewpoint of more excellent
conductivity.
The sheet resistance value is a value measured using Loresta-GP
(MCP-T600) (Mitsubishi Chemical Holdings Corporation) in conformity
with JIS K 7194 according to a four probe method.
The above-described conductive film can be used for various
applications and, for example, may be used for a touch panel or the
like.
Hereinafter, a preferred embodiment of a case where the conductive
film is applied to a touch panel will be described in detail.
<Touch Panel and Display Device Provided with a Touch
Panel>
The above-described conductive film can be suitably used for a
touch panel (preferably, a capacitance touch panel). More
specifically, the conductive film can be used as a member
constituting a touch panel and a conductive layer can be suitably
used for a detection electrode (sensor electrode) for sensing a
change in capacitance or a lead-out wiring (peripheral wiring) used
for applying a voltage to a detection electrode.
First Embodiment
Hereinafter, a first embodiment of a display device provided with a
touch panel to which the conductive film of the present invention
is applied will be described with reference to FIG. 1. FIG. 1 is a
sectional view schematically illustrating an example of a liquid
crystal display device provided with a touch panel of the present
invention. Further, FIG. 1 is a view schematically illustrated for
ease of understanding of a layer structure of the liquid crystal
display device provided with a touch panel and does not precisely
illustrates the disposition of each layer.
As illustrated in FIG. 1, a liquid crystal display device 10
provided with a touch panel includes a touch panel 16 configured of
a polarizer 12 and a first conductive layer 14A for a touch panel;
a liquid crystal cell 22 which includes a pair of bases 18A and 18B
for a liquid crystal cell and a liquid crystal layer 20 formed
between the pair of bases 18A and 18B for a liquid crystal cell;
and a polarizer 24 of the liquid crystal cell 22 on the opposite
side to the touch panel 16 side. The liquid crystal display device
10 provided with a touch panel illustrated in FIG. 1 has an on-cell
structure in which a first conductive layer 14A for a touch panel
is disposed between the polarizer 12 and the base 18B for a liquid
crystal cell. Moreover, in the liquid crystal display device 10
provided with a touch panel, a backlight (not illustrated) may be
disposed on the polarizer 24 on the opposite side to the liquid
crystal cell 22 side. Moreover, pressure sensitive adhesive layers
(not illustrated) may be disposed between each member. Further, if
necessary, the above-described protective film (for example, a
resin substrate or a glass substrate) may be disposed on the
surface of the polarizer 12 on the viewing side (the surface on the
opposite side to the first conductive layer 14A provided with a
touch panel).
Moreover, when a finger approaches and touches the surface (touch
surface) of the polarizer 12 in the liquid crystal display device
10 provided with a touch panel, the capacitance between the finger
and the detection electrode in the touch panel 16 is changed. Here,
when a change in capacitance of a predetermined value or greater is
detected, a position detection driver (not illustrated) detects the
position at which the change in capacitance is detected as an input
position. In this manner, the touch panel 16 is capable of
detecting an input position.
FIG. 2 is a plan view schematically illustrating an example of the
touch panel 16 used for the liquid crystal display device 10
provided with a touch panel illustrated in FIG. 1. FIG. 3 is an
enlarged sectional view taken along the line A-A of FIG. 2 and is a
view illustrating a portion of a first electrode array and a second
electrode array intersecting with each other.
The touch panel 16 includes is provided with the first conductive
layer 14A for a touch panel which is disposed on the polarizer 12,
and the first conductive layer 14A for a touch panel includes a
first electrode 30, a second electrode 32, a first connecting
portion 34, a second connecting portion 36, an insulating layer 38,
and a lead-out wring 40.
The first electrode 30, the second electrode 32, and the lead-out
wiring 40 contain fullerene functionalized carbon nanotubes. That
is, the first electrode 30, the second electrode 32, and the
lead-out wiring 40 correspond to the above-described conductive
layer. Further, the present invention is not limited to this
embodiment, and the conductive layer 14 for a touch panel may have
the above-described conductive layer containing fullerene
functionalized carbon nanotubes and the first connecting portion 34
and the second connecting portion 36 other than the first electrode
30, the second electrode 32, and the lead-out wiring 40 may contain
fullerene functionalized carbon nanotubes.
Hereinafter, each member included in the conductive layer 14 for a
touch panel will be described in detail.
More specifically, a plurality (four in FIG. 2) of first electrodes
30 are linearly arranged in an x direction (horizontal direction in
FIG. 2) and each of the electrodes is connected to the first
connecting portion 34 to form a first electrode array. In addition,
a plurality (four arrays in FIG. 2) of the first electrode arrays
are arranged in parallel with each other on the polarizer 12. The
first electrode arrays correspond to so-called detection
electrodes.
Further, a plurality (four in FIG. 2) of second electrodes 32 are
linearly arranged in a y direction (machine direction in FIG. 2)
perpendicular to the x direction and each of the electrodes is
connected to the second connecting portion 36 to form a second
electrode array. In addition, a plurality (four arrays in FIG. 2)
of the second electrode arrays are arranged in parallel with each
other on the polarizer 12. The second electrode arrays correspond
to so-called detection electrodes.
In addition, since the first electrode array and the second
electrode array are arranged by intersecting with each other such
that the first connecting portion 34 and the second connecting
portion 36 overlap each other, the first electrodes 30 and the
second electrodes 32 are arranged in a lattice shape on the
polarizer 12.
Moreover, since the first connecting portion 34 and the second
connecting portion 36 overlap each other, an insulating layer 38 is
interposed between the first connecting portion 34 and the second
connecting portion 36 in order to prevent conduction of the second
connecting portion 36 perpendicular to the first connecting portion
34 for insulation.
Moreover, since the lead-out wiring 40 connected to each of the
first electrode array and the second electrode array is disposed on
the polarizer 12 so that the first electrode 30, the second
electrode 32, and a control circuit (not illustrated) are connected
to each other through the lead-out wiring 40.
In addition, a region in which the first electrode 30 and the
second electrode 32 are present constitute an input region E.sub.1
(input region (sensing unit) capable of sensing contact of an
object) which is capable of performing an input operation by an
operator, and the lead-out wiring 40 and a flexible printed wiring
board (not illustrated) are disposed on an outer region E.sub.0
positioned outside of the input region E.sub.1.
The liquid crystal cell 22 includes at least the pair of bases 18A
and 18B for a liquid crystal cell and the liquid crystal layer 20
and may include other members (for example, a color filter, a TFT
Backplane, and the like).
Further, the liquid crystal display device 10 provided with a touch
panel may further include a light source.
Second Embodiment
Hereinafter, a second embodiment of a liquid crystal display device
provided with a touch panel to which the conductive film of the
present invention is applied will be described with reference to
FIG. 4.
As illustrated in FIG. 4, a liquid crystal display device 110
provided with a touch panel of the present invention includes a
polarizer 12, a second conductive layer 14B for a touch panel, a
pressure sensitive adhesive layer 42, a third conductive layer 14C
for a touch panel, a liquid crystal cell 22 which includes a pair
of bases 18A and 18B for a liquid crystal cell and a liquid crystal
layer 20 formed between the pair of bases 18A and 18B for a liquid
crystal cell, and a polarizer 24. The polarizer 12, the second
conductive layer 14B for a touch panel, the pressure sensitive
adhesive layer 42, and the third conductive layer 14C for a touch
panel constitute a touch panel 116. As described below, the second
conductive layer 14B for a touch panel, the above-described
conductive layer containing fullerene functionalized carbon
nanotubes may be exemplified. That is, the conductive film
including the polarizer 12 and the second conductive layer 14B for
a touch panel corresponds to the conductive film of the present
invention.
The liquid crystal display device 110 provided with a touch panel
illustrated in FIG. 4 has the same configurations as those of the
liquid crystal display device 10 provided with a touch panel
illustrated in FIG. 1 except for the touch panel 116. Therefore,
the same constituent elements are denoted by the same reference
numerals and the description thereof will not be repeated.
Hereinafter, the touch panel 116 will be mainly described in
detail.
FIG. 5 is a plan view illustrating a laminate X including the
polarizer 12 and the second conductive layer 14B for a touch panel
observed from the viewing side (polarizer 12 side). FIG. 6 is a
plan view illustrating a laminate Y including the third conductive
layer 14C for a touch panel and the liquid crystal cell 22 observed
from the viewing side.
As illustrated in FIG. 5, the laminate X includes the polarizer 12
and the second conductive layer 14B for a touch panel which is
disposed on the back surface side of the polarizer 12, and the
second conductive layer 14B for a touch panel includes a first
detection electrode 50 and a first lead-out wiring 52.
The first detection electrode 50 and the first lead-out wiring 52
include fullerene functionalized carbon nanotubes. That is, the
first detection electrode 50 and the first lead-out wiring 52
correspond to the above-described conductive layer. Further, the
present invention is not limited to this embodiment, and only the
first detection electrode 50 may be the above-described conductive
layer containing fullerene functionalized carbon nanotubes.
Further, the first detection electrode 50 plays a role of detecting
an input position in a Y direction of a finger of an operator
having approached the input region EI and has a function of
generating capacitance between the finger and the detection
electrode. The first detection electrode 50 is an electrode which
extends in the Y direction and is aligned in an X direction
perpendicular to the Y direction at a predetermined interval.
In addition, the first lead-out wiring 52 is disposed on the
polarizer 12 in the outer region E.sub.0. One end thereof is
electrically connected to the corresponding first detection
electrode 50 and the other end is electrically connected to a
flexible printed wiring board (not illustrated).
As illustrated in FIG. 6, the laminate Y includes the liquid
crystal cell 22 and the third conductive layer 14C for a touch
panel which is disposed on the back surface side of the liquid
crystal cell 22, and the third conductive layer 14C for a touch
panel includes a second detection electrode 54 and a second
lead-out wiring 56.
The second detection electrode 54 and the second lead-out wiring 56
include fullerene functionalized carbon nanotubes.
Further, the second detection electrode 54 plays a role of
detecting an input position in the X direction of a finger of an
operator having approached the input region EI and has a function
of generating capacitance between the finger and the detection
electrode. The second detection electrode 54 is an electrode which
extends in the X direction and is aligned in the Y direction at a
predetermined interval.
In addition, the second lead-out wiring 56 is disposed on the
polarizer 22 in the outer region E.sub.0. One end thereof is
electrically connected to the corresponding second detection
electrode 54 and the other end is electrically connected to a
flexible printed wiring board (not illustrated).
As illustrated in FIGS. 5 and 6, the first detection electrode 50
and the second detection electrode 54 are disposed so as to be
orthogonal to each other when the liquid crystal display device 110
provided with a touch panel is observed from the viewing side.
A region in which the first electrode 50 and the second electrode
54 are present constitute an input region EI (input region (sensing
unit) capable of sensing contact of an object) which is capable of
performing an input operation by an operator, and the first
lead-out wiring 52 and the second lead-out wiring 56 are disposed
on an outer region E.sub.0 positioned outside of the input region
EI.
Further, the pressure sensitive adhesive layer 42 is a layer
connecting members to each other and a known pressure sensitive
adhesive layer can be used.
Third Embodiment
Hereinafter, a third embodiment of a liquid crystal display device
provided with a touch panel to which the conductive film of the
present invention is applied will be described with reference to
FIG. 7.
As illustrated in FIG. 7, a liquid crystal display device 210
provided with a touch panel of the present invention includes a
polarizer 12, a second conductive layer 14B for a touch panel, a
pair of bases 18A and 18B for a liquid crystal cell, a liquid
crystal layer 20 formed between the pair of bases 18A and 18B for a
liquid crystal cell, a third conductive layer 14C for a touch
panel, and a polarizer 24. The polarizer 12, the second conductive
layer 14B for a touch panel, and the third conductive layer 14C for
a touch panel constitute a touch panel.
The liquid crystal display device 210 provided with a touch panel
illustrated in FIG. 7 has the same configurations as those of the
liquid crystal display device 110 provided with a touch panel
illustrated in FIG. 4 except that disposition of each layer varies.
Therefore, the same constituent elements are denoted by the same
reference numerals and the description thereof will not be
repeated.
In the liquid crystal display device 210 provided with a touch
panel, the first detection electrode 50 in the second conductive
layer 14B for a touch panel and the second detection electrode 54
in the third conductive layer 14C for a touch panel are disposed so
as to be orthogonal to each other similar to the liquid crystal
display device 110 provided with a touch panel illustrated in FIG.
4.
(Use for Other Applications)
As described above, the conductive film of the present invention
may include a .lamda./4 plate. In this case, the obtained
conductive film functions as a so-called circularly polarized light
plate, becomes a constituent element of a touch panel when disposed
on an organic EL display device, and functions as a circularly
polarized light plate that prevents reflection of external
light.
As a specific embodiment, an organic EL display device 80 provided
with a touch panel including a polarizer 12, a .lamda./4 plate 60,
a first conductive layer 14A for a touch panel, and an organic EL
display device 70 as illustrated in FIG. 8 may be exemplified. The
polarizer 12, the .lamda./4 plate 60, and the first conductive
layer 14A for a touch panel constitute the conductive film of the
present invention and an angle formed by a transmission axis of the
polarizer 12 and an in-plane slow axis of the .lamda./4 plate 60 is
45.degree..
In addition, as another specific embodiment, an organic EL display
device 180 provided with a touch panel including a polarizer 12, a
.lamda./4 plate 60, a second conductive layer 14B for a touch
panel, a pressure sensitive adhesive layer 42, a third conductive
layer 14C for a touch panel, and an organic EL display device 70 as
illustrated in FIG. 9 may be exemplified. An angle formed by a
transmission axis of the polarizer 12 and an in-plane slow axis of
the .lamda./4 plate 60 is 45.degree..
EXAMPLES
Hereinafter, the present invention will be described in more detail
with reference to examples, but the present invention is not
limited thereto.
Example 1
(Preparation of Polarizer Provided with Protective Film)
A commercially available cellulose acylate film (FUJITAC TJ25UL,
manufactured by Fujifilm Corporation) was immersed in 1.5 mol/L of
a NaOH aqueous solution (saponification solution) at 55.degree. C.
for 2 minutes and the film was washed with water. Thereafter, the
film was immersed in 0.05 mol/L of a sulfuric acid aqueous solution
at 25.degree. C. for 30 seconds and then exposed to flowing water
for 30 seconds so that the state of the film was set to be neutral.
Further, draining was carried out three times using an air knife,
the film was allowed to stay for 15 seconds in a drying zone at
70.degree. C. after water was dropped and then dried, and then a
film subjected to a saponification treatment was prepared.
The film subjected to a saponification treatment was bonded to one
surface of a polarizer (polyvinyl alcohol-based resin
(PVA)-containing polarizer) having a film thickness of 8 .mu.m
using a polyvinyl alcohol-based adhesive and dried at 70.degree. C.
for 10 minutes, thereby preparing a polarizer provided with a
protective film. Here, the film was disposed such that the
conveyance direction of the film and the transmission axis of the
polarizer were orthogonal to each other.
(Synthesis of Fullerene Functionalized Carbon Nanotubes
(CBFFCNT))
CBFFCNT was synthesized from carbon monoxide as a carbon source
using perrocene as a catalyst particle source and water vapor
and/or carbon dioxide as a reagent (one or plural kinds).
Hereinafter, the conditions are described in detail.
Carbon source: CO. Catalyst particle source: ferrocene (partial
pressure of vapor in reactor: 0.7 Pa). Use oven temperature:
800.degree. C., 1000.degree. C., and 1150.degree. C. Use flow rate:
internal flow (including ferrocene vapor) of CO at 300 ccm and
external flow of CO at 100 ccm. Reagent: water vapor (150 and 270
ppm) and/or carbon dioxide (1500 to 12000 ppm).
The synthesis was performed in the manner described in FIG. 3A of
JP2009-515804A. In this embodiment, catalyst particles were
instantly grown by ferrocene vapor decomposition. The precursor was
evaporated by passing CO at room temperature through a cartridge
(4) filled with ferrocene powder from a gas cylinder (2) (at a flow
rate of 300 ccm). Thereafter, the flow containing ferrocene vapor
was introduced to a high-temperature zone of a ceramic tube reactor
through a water-cooled probe (5) and then mixed with the additional
CO flow (1) at a flow rate of 100 ccm.
Subsequently, an oxidizing etchant (for example, water and/or
carbon dioxide) was introduced thereto together with a carbon
source. In addition, the partial pressure of ferrocene vapor in the
reactor was maintained to 0.7 Pa. Thereafter, the set temperature
of the reactor wall was changed from 800.degree. C. to 1150.degree.
C.
Aerosol products were recovered at the downstream of the reactor by
any of a silver disc filter or a grid of a transmission electron
microscope (TEM). It was confirmed that CBFFCNT in which carbon
nanotubes and fullerenes were covalently bonded to each other was
present in these aerosol products.
A conductive layer containing CBFFCNT was prepared on a filter by
filtering the obtained aerosols using a filter of nitrocellulose
having a diameter of 2.45 cm. In addition, the temperature of the
filter surface at the time of filtration was 45.degree. C.
Next, the conductive layer disposed on the filter was transferred
to the surface of the polarizer provided with a protective film and
the conductive layer (thickness: 10 .mu.m) was disposed on the
polarizer.
Subsequently, a hard coat layer (thickness: 6 .mu.m) was prepared
on the obtained conductive layer according to the method described
below, thereby obtaining a conductive film.
(Procedures for Preparing Hard Coat Layer)
4 parts by mass of IRGACURE 184 (photopolymerization initiator,
manufactured by BASF Japan Ltd.) was added to a mixed solvent of
methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) and
dissolved therein while the solution was stirred, thereby preparing
a solution having 40% by mass of a final solid content.
Pentaerythritol triacrylate (PETA), U-4HA (tetrafunctional urethane
oligomer, weight-average molecular weight of 600, manufactured by
Shin-Nakamura Chemical Co., Ltd.), U-15HA (15 functional urethane
oligomer, weight-average molecular weight of 2300, manufactured by
Shin-Nakamura Chemical Co., Ltd.), and a polymer (7975-D41, acrylic
double bond equivalent of 250, weight-average molecular weight of
15000, manufactured by Hitachi Chemical Co., Ltd.) were added, as
resin components, to the solution at a solid content ratio of 25
parts by mass:25 parts by mass:40 parts by mass:10 parts by mass
and the solution was stirred. A leveling agent (trade name:
MEGAFACE F-477, manufactured by DIC Corporation) was added to the
solution at a solid content ratio of 0.2 parts by mass and the
solution was stirred, thereby preparing a composition for forming a
hard coat layer.
The conductive layer was coated with the composition for forming a
hard coat layer according to slit reverse coating to form a coated
film. The obtained coated film was dried at 70.degree. C. for 1
minute, irradiated with ultraviolet rays at an ultraviolet
irradiation dose of 150 mJ/cm.sup.2, and cured, thereby forming a
hard coat layer having a thickness of 6 .mu.m.
Examples 2 to 14
Conductive films were obtained in the same manner as in Example 1
except that the type of polarizer provided with a protective film
used in Example 1 was changed.
Further, in Examples 2 to 10, the type of protective film and the
thickness of polarizer were changed and then conductive films were
prepared in the same manner as in Example 1.
Moreover, in Examples 11 and 12, conductive films were prepared in
the same manner as in Example 1 except that a laminate Z including
an acrylic film and a polarizer (thickness: 5 .mu.m) and a laminate
W including an acrylic film and a polarizer (thickness: 3 .mu.m),
serving as coating type PVA polarizer-containing laminates
described below, were used in place of the polarizer provided with
a protective film.
Moreover, in Examples 13 and 14, conductive films were prepared in
the same manner as in Example 1 except that a laminate V including
a cellulose acylate film and a polarizer (thickness: 5 .mu.m) and a
laminate P including a cellulose acylate film and a polarizer
(thickness: 3 .mu.m), serving as coating type PVA
polarizer-containing laminates described below, were used in place
of the polarizer provided with a protective film.
(Preparation of Coating Type PVA Polarizer-Containing Laminate)
A laminate (laminate Z) including an acrylic film and a polarizer
(thickness: 5 .mu.m) was prepared in the same manner as in Example
5 (paragraph 0161) of JP4691205B except that an acrylic film
(Technolloy S001G, manufactured by Sumitomo Chemical Company Ltd.)
was used in place of a triacetyl cellulose (TAC) film. Further, a
laminate (laminate W) including an acrylic film and a polarizer
(thickness: 3 .mu.m) was prepared in the same manner as in
JP4691205B except that the thickness of the polarizer was changed
into 3 .mu.m from 5 .mu.m.
Moreover, a laminate (laminate V) including a cellulose acylate
film and a polarizer (thickness: 5 .mu.m) was prepared using a
cellulose acylate film (TJ25UL, manufactured by Fujifilm
Corporation) in place of the acrylic film. Further, a laminate
(laminate P) including a cellulose acylate film and a polarizer
(thickness: 3 .mu.m) was prepared in the same manner as in
JP4691205B except that the thickness of the polarizer was changed
into 3 .mu.m from 5 .mu.m.
The following evaluation was performed using conductive films of
the examples and the comparative examples obtained in the
above-described manner. Further, the obtained results are
collectively listed in Table 1.
In regard to Comparative Examples 1 and 2, a moisture heat
durability test described below was performed using the
above-described laminate Z and laminate W.
<Moisture Heat Durability Test>
Samples having a size of 50 mm.times.50 mm were cut out from the
prepared conductive films, and hard coat layers (polarizers in
Comparative Examples 1 and 2) in conductive films were bonded to
glass plates using a pressure sensitive adhesive. The prepared
samples were treated at -30.degree. C. for 30 minutes, the
temperature thereof was increased to 70.degree. C. at a rate of
5.degree. C./minute, and the samples were treated at 70.degree. C.
for 30 minutes, and then the temperature thereof was decreased to
-30.degree. C. at a rate of -5.degree. C./minute. These series of
operations were repeated 200 times. The series of operations were
finished and the conductive films were visually observed. A case
where cracks were not found in a polarizer was evaluated as "A" and
a case where cracks were found in a polarizer was evaluated as
"B".
<Measurement of Transmittance and Polarization Degree>
A single transmittance T (%), a parallel transmittance Tp (%), and
an orthogonal transmittance Tc (%) of the prepared conductive films
were measured using an ultraviolet and visible spectrophotometer
(V7100, manufactured by JASCO Corporation). These transmittances T,
Tp, and Tc are Y values which were measured by a two-degree field
of view (C light source) of JIS Z 8701 and on which visibility
correction was performed.
Next, a polarization degree P was acquired according to the
following equation using the above-described transmittances.
Polarization degree P (%)={(Tp-Tc)/(Tp+Tc)}1/2.times.100
Moreover, the "transmittance (%)" in Table 1 shown below
corresponds to the above-described "single transmittance (%)".
Further, the above-described parallel transmittance indicates a
transmittance of a sample obtained, using two sheets of conductive
films, by laminating the two sheets of conductive films on each
other such that transmittance axes of polarizers in the conductive
films are parallel with each other. Further, the above-described
orthogonal transmittance indicates a transmittance of a sample
obtained, using two sheets of conductive films, by laminating the
two sheets of conductive films on each other such that transmission
axes of polarizers in the conductive films are orthogonal to each
other.
<Measurement of Sheet Resistance Value>
Samples having a size of 80 mm.times.50 mm were cut out from the
prepared conductive films and the sheet resistance values were
measured using Loresta-GP (MCP-T600) (Mitsubishi Chemical Holdings
Corporation) in conformity with JIS K 7194 according to a four
probe method.
In Table 1, the "PVA" indicates a polyvinyl alcohol-based
resin.
In Table 1, the "HC layer" indicates a hard coat layer.
The types of supports represented by symbols in the columns of
"protective film" in Table 1 are as follows. TJ25: cellulose
acylate film (FUJITAC TJ25UL, manufactured by Fujifilm Corporation)
Sample A: referred to the description below TG40: cellulose acylate
film (FUJITAC TG40UL, manufactured by Fujifilm Corporation) ZRD40:
cellulose acylate film (FUJITAC ZRD40, manufactured by Fujifilm
Corporation) Cycloolefine: cycloolefine film (ZF14, manufactured by
Zeon Corporation) Acryl: acrylic film (Technolloy S001G,
manufactured by Sumitomo Chemical Company Ltd.)
(Preparation of Sample A)
(Preparation of Core Layer Cellulose Acylate Dope)
The following composition was put into a mixing tank and stirred
and each component was dissolved therein, and then a cellulose
acetate solution was prepared.
TABLE-US-00001 Cellulose acetate having an acetyl 100 parts by mass
substitution degree of 2.88 Ester oligomer A 10 parts by mass The
following additive B 4 parts by mass Ultraviolet absorbing agent C
2 parts by mass Methylene chloride C (first solvent) 430 parts by
mass Methanol (second solvent) 64 parts by mass
(Ester Oligomer A)
A copolymer (terminal is formed of an acetyl group) of an aromatic
dicarboxylic acid (ratio of adipic acid:phthalic acid is 3:7) and a
diol (ethylene glycol). Molecular weight of 1000
(Additive B)
##STR00011##
(Ultraviolet Absorbing Agent C)
##STR00012##
(Preparation of Outer Layer Cellulose Acylate Dope)
An outer layer cellulose acetate solution was prepared by adding 10
parts by mass of the following matting agent solution having the
following composition to 90 parts by mass of the above-described
core layer cellulose acylate dope.
TABLE-US-00002 Silica particles having average particle size 2
parts by mass of 20 nm (AEROSIL R972, manufactured by Nippon
Aerosil Co., Ltd.) Methylene chloride (first solvent) 76 parts by
mass Methanol (second solvent) 11 parts by mass Core layer
cellulose acylate dope 1 part by mass
(Preparation of Cellulose Acylate Film)
The core layer cellulose acylate dope and outer layer cellulose
acylate dopes on both side of the core layer cellulose acylate
dope, that are, three layers were cast on a drum at 20.degree. C.
from a casting port at the same time. The outer layers were peeled
off in a state in which the solvent content was 20% by mass, both
ends of the film in the width direction were fixed with tenter
clips, and the film was dried while being stretched to 1.1 times in
the transverse direction in a state in which the residual solvent
was in a range of 3% to 15%. Thereafter, the film was further dried
by being conveyed between rolls of a heat treatment device, thereby
preparing a cellulose acylate film (sample A) having a thickness of
40 .mu.m.
TABLE-US-00003 TABLE 1 Conductive film Evaluation Polarizer
Polarization Sheet resis- Type of Thickness Conductive HC Moisture
heat Transmittance degree tance value protective film Type (.mu.m)
layer layer durability test (%) (%) (.OMEGA./.quadrature.) Example
1 TJ25 PVA 8 Present Present A 43.2 99.996 80 Example 2 TJ25 PVA 15
Present Present A 42.9 99.997 90 Example 3 Sample A PVA 8 Present
Present A 42.7 99.996 100 Example 4 Sample A PVA 15 Present Present
A 42.2 99.997 110 Example 5 TG40 PVA 8 Present Present A 42.8
99.996 95 Example 6 TG40 PVA 15 Present Present A 42.3 99.997 100
Example 7 ZRD40 PVA 8 Present Present A 42.9 99.994 100 Example 8
ZRD40 PVA 15 Present Present A 42.3 99.992 110 Example 9
Cycloolefine PVA 8 Present Present A 43 99.993 90 Example 10
Cycloolefine PVA 15 Present Present A 42.5 99.994 100 Example 11
Acryl Coating type 5 Present Present A 43.2 99.99 80 PVA Example 12
Acryl Coating type 3 Present Present A 42.9 99.992 75 PVA Example
13 TJ25 Coating type 5 Present Present A 43.1 99.99 85 PVA Example
14 TJ25 Coating type 3 Present Present A 42.8 99.992 80 PVA
Comparative Acryl Coating type 5 Absent Absent B -- -- -- Example 1
PVA Comparative Acryl Coating type 3 Absent Absent B -- -- --
Example 2 PVA
As listed in Table 1, in the conductive films of the present
invention, cracking in polarizers was suppressed during the
moisture heat durability test and thus performance degradation did
not occur in the polarizers.
Meanwhile, in Comparative Examples 1 and 2 in which conductive
layers were not disposed, occurrence of cracks was found in
polarizers during the moisture heat durability test.
In addition, in Examples 1 to 14, various evaluations were
performed using conductive films respectively including a hard coat
layer, and cracking in polarizers was suppressed during the
moisture heat durability test even in a case of conductive films
which did not have a hard coat layer and thus performance
degradation did not occur in the polarizers.
Example 15: Preparation of Touch Panel
Conductive layers were disposed on a polarizer provided with a
protective film according to the procedures of Example 1. Next, by
following procedures described below, as illustrated in FIG. 5,
conductive layers in other portions were removed through etching by
leaving only the conductive layers positioned in portions of the
first detection electrodes and the first lead-out wirings.
Subsequently, hard coat layers were respectively disposed on
patterned conductive layers in the same manner as in Example 1,
thereby obtaining a conductive film. Further, the length of the
first detection electrode was 170 mm and the number of the first
detection electrodes was 32.
Next, a third conductive layer 14C for a touch panel in which a
conductive layer including CBFFCNT was present in the positions of
the second detection electrode and the second lead-out wiring as
illustrated in FIG. 6 was prepared by referring to the procedures
of Example 1. The length of the second detection electrode included
in the third conductive layer for a touch panel was 300 mm and the
number of the second detection electrodes was 56.
Next, various members were bonded to each other using the obtained
conductive film and a liquid crystal cell in order of lamination
illustrated in FIG. 4, thereby obtaining a display device provided
with a touch panel illustrated in FIG. 4.
(Method of Etching Conductive Layer)
A desired pattern was formed on a conductive layer disposed on a
polarizer according to a laser etching method (for example, see
WO2013/176155A) using a UV laser.
In the description above, the conductive layer was disposed on the
polarizer and subjected to an etching treatment, and then a hard
coat layer was disposed on the patterned conductive layer.
Alternatively, after a conductive layer and a hard coat layer were
disposed on a polarizer, a conductive layer with a predetermined
pattern was prepared according to the above-described etching
method, and then a display device provided with a touch panel was
prepared in the above-described manner.
In addition, a display device provided with a touch panel
illustrated in FIG. 1 was obtained by disposing a conductive layer
on one surface of a polarizer, changing the etching pattern of the
conductive layer, changing the pattern shown in the first
conductive layer 14A for a touch panel illustrated in FIG. 2,
preparing a predetermined conductive layer, and bonding various
members to each other in order of lamination illustrated in FIG.
1.
Further, a display device provided with a touch panel illustrated
in FIG. 7 was obtained by changing the position of the conductive
layer.
Further, the polarizer provided with a protective film used in
Example 1 was used in the above, but various display device
provided with a touch panel were obtained in the same manner as
described above even when the polarizers provided with a protective
film used in Examples 2 to 12.
In the preparation of Example 1, a conductive film including a
.lamda./4 plate was prepared by disposing a .lamda./4 plate between
the polarizer and the conductive layer. At this time, the
conductive layer was adjusted so as to have a pattern shown in the
first conductive layer 14A for a touch panel illustrated in FIG.
2.
The obtained conductive film including a .lamda./4 plate was
disposed on an organic EL display device as illustrated in FIG.
8.
In addition, the method of preparing a .lamda./4 plate was as
follows.
(Alkali Saponification Treatment)
A cellulose acylate film (TG40UL, manufactured by Fujifilm
Corporation) was allowed to pass through an induction heating roll
at 60.degree. C., the temperature of the film surface was increased
to 40.degree. C., the band surface of the film was coated with an
alkali solution having the composition described below at a coating
amount of 14 ml/m.sup.2 using a bar coater, and then the film was
conveyed for 10 seconds under a steam-type far-infrared heater
(manufactured by NORITAKE Co., LTD.) heated to 110.degree. C. Next,
the surface thereof was coated with 3 ml/m2 of pure water using a
bar coater in the same manner. Subsequently, washing with water
using a fountain coater and draining using an air knife were
repeatedly performed on the film three times and then the film was
conveyed for 10 seconds to a drying zone at 70.degree. C. to be
dried, thereby preparing a cellulose acylate film subjected to an
alkali saponification treatment.
Composition of Alkali Solution
TABLE-US-00004 Potassium hydroxide 4.7 parts by mass Water 15.8
parts by mass Isopropanol 63.7 parts by mass Surfactant SF-1:
C14H29O (CH2CH2O)20H 1.0 part by mass Propylene glycol 14.8 parts
by mass
(Formation of Alignment Layer)
The surface of the cellulose acylate film subjected to the alkali
saponification treatment was continuously coated with an alignment
film coating solution (A) having the composition described below
using a #14 wire bar. The film was dried with warm air at
60.degree. C. for 60 seconds and further dried with warm air at
100.degree. C. for 120 seconds. The saponification degree of
modified polyvinyl alcohol used was 96.8%.
Composition of Alignment Film Coating Solution (A)
TABLE-US-00005 Modified polyvinyl alcohol 1 described below 10
parts by mass Water 308 parts by mass Methanol 70 parts by mass
Isopropanol 29 parts by mass Photopolymerization initiator
(IRGACURE 2959, 0.8 parts by mass manufactured by Ciba Specialty
Chemical K.K.)
[Modified Polyvinyl Alcohol 1]
##STR00013##
(Formation of First Optical Anisotropic Layer)
The prepared alignment film was continuously subjected to a rubbing
treatment. At this time, the longitudinal direction and the
conveyance direction of the long film were parallel with each other
and the angle formed by the film longitudinal direction and a
rotating shaft of a rubbing roller was set to 75.degree.
(clockwise) (when the film longitudinal direction was set to
90.degree., the rotation shaft of the rubbing roller was
15.degree.).
The above-described alignment film was continuously coated with the
optically anisotropic layer coating solution (A) including a
discotic liquid crystal compound having the composition described
below using a #5.0 wire bar and treated under the following
conditions, and a retardation plate (F1) having a first optically
anisotropic layer (H) was prepared. In addition, the conveyance
speed (V) of the film was set to 26 m/min. For the purpose of
drying the solvent of the coating solution and alignment aging of
the discotic liquid crystal compound, the plate was heated with
warm air at 130.degree. C. for 90 seconds, then heated further with
warm air at 100.degree. C. for 60 seconds, and irradiated with UV
rays at 80.degree. C. to fix the alignment of the liquid crystal
compound. The thickness of the first optically anisotropic layer
(H) was 2.0 .mu.m. It was confirmed that the average tilt angle of
the disk plane of the discotic liquid crystal (DLC) compound with
respect to the film surface was 90.degree. and the DLC compound was
aligned vertically to the film surface. The slow axis was parallel
with the rotating shaft of the rubbing roller and the angle thereof
was 15.degree. when the film longitudinal direction was set to
90.degree. (film width direction was set to 0.degree.).
Composition of Optically Anisotropic Layer Coating Solution (A)
TABLE-US-00006 Discotic liquid crystal 1 80 parts by mass Discotic
liquid crystal 2 20 parts by mass Alignment film interface
alignment agent 1 0.55 parts by mass Alignment film interface
alignment agent 2 0.05 parts by mass Fluorine-containing compound
(FP-1) 0.1 parts by mass Modified trimethylol propane triacrylate
10 parts by mass Photopolymerization initiator 3.0 parts by mass
(IRGACURE 907, manufactured by Ciba Specialty Chemical K.K.) Methyl
ethyl ketone 200 parts by mass
Discotic Liquid Crystal 1
##STR00014##
Discotic Liquid Crystal 2
##STR00015##
Alignment Film Interface Alignment Agent 1
##STR00016##
Alignment Film Interface Alignment Agent 2
##STR00017##
Fluorine-Containing Compound (FP-1)
##STR00018##
Preparation of Retardation Plate (F2)
(Preparation of Peelable Support)
A peelable support was prepared in the same manner as the
production of the alignment film except that the alignment film was
prepared as described below without applying an alkali
saponification treatment to the above-described cellulose acylate
film.
(Formation of Alignment Film)
The cellulose acylate film was continuously coated with an
alignment film coating solution (B) having the following
composition using a #14 wire bar. The film was dried with warm air
at 60.degree. C. for 60 seconds and further dried at 100.degree. C.
for 120 seconds.
Composition of Alignment Film Coating Solution (B)
TABLE-US-00007 Modified polyvinyl alcohol 2 described below 10
parts by mass Water 371 parts by mass Methanol 119 parts by mass
Glutaraldehyde (crosslinking agent) 0.5 parts by mass Citric acid
ester (AS3, manufactured by 0.175 parts by mass SANKYO CHEMICAL
Co., Ltd.) Photopolymerization initiator (IRGACURE 2959, 2.0 parts
by mass manufactured by Ciba Specialty Chemical K.K.)
[Modified Polyvinyl Alcohol 2]
##STR00019##
(Formation of Second Optically Anisotropic Layer (Q))
The prepared alignment film was continuously subjected to a rubbing
treatment. At this time, the longitudinal direction and the
conveyance direction of the long film were parallel with each other
and the angle formed by the film longitudinal direction and a
rotating shaft of a rubbing roller was set to 75.degree.
(clockwise) (when the film longitudinal direction was set to
90.degree., the rotation shaft of the rubbing roller was
15.degree.).
The above-described alignment film was continuously coated with the
optically anisotropic layer coating solution (B) including a
rod-like liquid crystal compound having the composition described
below using a #2.2 wire bar and treated under the following
conditions, and a retardation plate (F2) having a second optically
anisotropic layer (Q) was prepared. In addition, the conveyance
speed (V) of the film was set to 26 m/min. For the purpose of
drying the solvent of the coating solution and alignment aging of
the rod-like liquid crystal compound, the plate was heated with
warm air at 60.degree. C. for 60 seconds and irradiated with UV
rays at 60.degree. C. to fix the alignment of the liquid crystal
compound. The thickness of the second optically anisotropic layer
(Q) was 0.8 .mu.m. It was confirmed that the average tilt angle of
the long axis of the rod-like liquid crystal compound with respect
to the film surface was 0.degree. and the liquid crystal compound
was aligned horizontally to the film surface. The slow axis was
orthogonal to the rotating shaft of the rubbing roller and the
angle thereof was 105.degree. when the film longitudinal direction
was set to 90.degree. (film width direction was set to
0.degree.).
Composition of Optically Anisotropic Layer Coating Solution (B)
TABLE-US-00008 Rod-like liquid crystal compound 1 80 parts by mass
Rod-like liquid crystal compound 2 2.0 parts by mass
Photopolymerization initiator (IRGACURE 907, 3 parts by mass
manufactured by Ciba Specialty Chemical K.K.) Sensitizer (KAYACURE
DETX, manufactured by 1 part by mass Nippon Kayaku Co., Ltd.)
Fluorine-containing compound (FP-2) 0.3 parts by mass Methyl ethyl
ketone 193 parts by mass
[Rod-Like Liquid Crystal Compound 1]
##STR00020##
[Rod-Like Liquid Crystal Compound 2]
##STR00021##
[Fluorine-Containing Compound (FP-2)]
##STR00022##
(Preparation of .lamda./4 Plate)
The surface of the above-described retardation plate (F1) coated
with the first optically anisotropic layer (H) and the surface of
the above-described retardation plate (F2) coated with the second
optically anisotropic layer (Q) were continuously bonded to each
other using a pressure sensitive adhesive layer, and the
above-described peelable support was peeled off between the
cellulose acylate film (T1) and the alignment film. In this manner,
a long circularly polarizing plate (P2) was prepared. In addition,
an absorption axis of the polarizer in the conductive film
coincides with the longitudinal direction of the polarizer and the
angle formed by the absorption axis of the polarizer and the slow
axis of the second optically anisotropic layer (Q) was
15.degree..
Moreover, the in-plane retardation of the first optically
anisotropic layer (H) at a wavelength of 550 nm was 275 nm and the
in-plane retardation of the second optically anisotropic layer (Q)
at a wavelength of 550 nm was 137.5 nm. In the conductive film, the
first optically anisotropic layer (H) was disposed on the polarizer
side.
EXPLANATION OF REFERENCES
10, 110, 210: display device provided with touch panel 12, 24:
polarizer 14A: first conductive layer for touch panel 14B: second
conductive layer for touch panel 14C: third conductive layer for
touch panel 16, 116: touch panel 18A, 18B: base for liquid crystal
cell 20: liquid crystal layer 22: liquid crystal cell 30: first
electrode 32: second electrode 34: first connecting portion 36:
second connecting portion 38: insulating layer 40: lead-out wiring
42: pressure sensitive adhesive layer 50: first detection electrode
52: first lead-out wiring 54: second detection electrode 56: second
lead-out wiring 60: .lamda./4 plate 70: organic EL display device
80, 180: organic EL display device provided with touch panel
* * * * *